CN109400903A - A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material and preparation method thereof - Google Patents
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material and preparation method thereof Download PDFInfo
- Publication number
- CN109400903A CN109400903A CN201811322806.7A CN201811322806A CN109400903A CN 109400903 A CN109400903 A CN 109400903A CN 201811322806 A CN201811322806 A CN 201811322806A CN 109400903 A CN109400903 A CN 109400903A
- Authority
- CN
- China
- Prior art keywords
- mofs
- metal
- cage modle
- poss
- tpa
- 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.)
- Granted
Links
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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention provides a kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material and preparation method thereof.MOFs of the present invention occurs polymerization reaction with cage modle polysilsesquioxane and prepares POSS/MOFs hybrid material after the modification of vinyl function monomer.The method of the present invention preparation manipulation is simple, and reaction condition is milder, product yield high, easily separated and purification.Gained hybrid material has a variety of pore structures, can solve the problems, such as MOFs material processing difficulties and be not easy device；So that gained hybrid material is conducive to processing and device, and can be applied to gas absorption with separate, the fields such as ion and Dye Adsorption, carrier；Applied to Dye Adsorption field, there is preferable adsorption effect and reusable.
Description
Technical field
The present invention relates to a kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid materials
And preparation method thereof, belong to new material technology field.
Background technique
Cage modle polysilsesquioxane (POSS) is a kind of inorganic-organic hybrid molecule with nano-scale, and general formula is
(RSiO1.5)n, n=6,8,10 or 12 etc., R is the organic groups such as alkyl, alkenyl, amino.Cage modle polysilsesquioxane molecule tool
There is rigid cage type symmetrical structure, Si-O-Si skeleton structure assigns the good thermal stability of cage modle polysilsesquioxane molecule, Gao Jie
The performances such as electrical and anti-flammability.Vertex in cage modle polysilsesquioxane molecular structure can functionalization, pass through reactive R group
It is copolymerized, is grafted or cross-linking reaction with other monomers or polymer, so as to design and prepare new material, by molecule
Cage modle polysilsesquioxane is introduced in structure or composite material, and use temperature, mechanical property, the processability of material can be improved
Can, and make material that there is significant delayed combustion characteristic, obtaining has the polymer-modified of different performance.
Metal-organic framework material is that one kind is formed by metal ion or ion cluster and organic ligand by Coordinate self-assembly
Inorganic-organic Hybrid Materials, have specific topological structure and pore structure.Metal-organic framework material is more due to structure
Sample, porosity be high, the regulatable advantage in duct and in gas absorption and separation, heterocatalysis, drug delivery, bio-sensing etc.
Field has a good application prospect.However, such material is crystal-type powder or particle, processing difficulties are not easy device；For
This problem is solved, metal-organic framework material can be improved to the processing performance and usability of material in conjunction with other materials
Can, such as metal-organic backbone and graphene oxide, mesoporous silicon material hydridization, or by metal-organic backbone be dispersed in polymer,
Improve the processing performance and service performance of material in aerogel material.But in above-mentioned material preparation, metal-organic backbone material
Material is present in material in a manner of physical blending, cannot reach good dispersion on a molecular scale, though it can be to a certain degree
Improve the processing of metal-organic framework material and service performance, but acquired material processing and service performance it is still not good enough；And
And metal-organic framework material is present in material in a manner of physical blending, is easy mutually to separate, is also unfavorable for the porous knot of material
The maintenance and raising of structure, to also will affect its subsequent application effect.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provides a kind of cage modle polysilsesquioxane/metal -2- amino to benzene
Dioctyl phthalate metal-organic framework hybrid material.The present invention is by two kinds of rigidity of cage modle polysilsesquioxane and metal -2- organic framework material
Porous material combined in a manner of chemical covalent bonds, cage modle polysilsesquioxane play on a molecular scale disperse and support gold
The effect of category-organic framework material, while new pore structure can be constructed；Gained hybrid material of the invention is crosslinking net knot
Structure has a variety of pore structures, can be by changing cage modle polysilsesquioxane and metal-organic framework material mass ratio to hydridization
Material composition and pore structure are regulated and controled, and can be solved metal-organic framework material material processing difficulties and are not easy device
Problem；So that gained hybrid material is conducive to processing and device, and can be applied to gas absorption with separate, ion and Dye Adsorption,
The fields such as carrier；Applied to Dye Adsorption field, there is preferable adsorption effect and reusable.
The present invention also provides cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid materials
Preparation method.The method of the present invention preparation manipulation is simple, and reaction condition is milder, product yield high, easily separated and purification.
Term explanation:
Metal -2- amino terephthalic acid (TPA) organic frame (MOFs), structural formula is write a Chinese character in simplified form are as follows: metal organic frame-NH2；Gold
It include multiple NH in category -2- amino terephthalic acid (TPA) organic frame2, structural formula " metal organic frame-NH2" only represent metal and have
Contain NH in machine frame2, contain NH without indicating2Number.
Technical scheme is as follows:
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/
MOFs), which is figure reticular structure, includes such as flowering structure: metal organic frame-NH in molecular structure2Structure
The structural unit of unit grafting cage modle polysilsesquioxane；Metal organic frame-the NH2For metal -2- amino terephthaldehyde
Sour organic frame has structure shown in Formulas I or II；
Wherein, in Formulas I structural formula, M Al3+Ion cluster, Fe3+Ion cluster, Zr4+Ion cluster or Cr3+Ion
Cluster,Represent ligand 2-amino terephthalic acid (TPA)；In Formula II structural formula, M1 Zn2+Ion cluster,Represent ligand
2-amino terephthalic acid (TPA)s；
The cage modle polysilsesquioxane has structure shown in following formula III:
Wherein, in formula III structural formula, R is vinyl, aminopropyl or mercapto propyl；
When the R of cage modle polysilsesquioxane is vinyl, the metal organic frame-NH2Structural unit and cage modle
The connection bridged bond of the structural unit of polysilsesquioxane is-NHCOCH (CH3)(CH2)3–；When the R of cage modle polysilsesquioxane is
When aminopropyl, the metal organic frame-NH2Structural unit and cage modle polysilsesquioxane structural unit connection bridged bond
For-NHCOCH (CH3)CH2NH(CH2)3–；When the R of cage modle polysilsesquioxane is mercapto propyl, the metal organic frame-NH2
Structural unit and cage modle polysilsesquioxane structural unit connection bridged bond be-NHCOCH (CH3)CH2S(CH2)3–。
Above-mentioned cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
(1) preparation of the MOFs of vinyl functionalization；
Metal -2- amino terephthalic acid (TPA) organic frame (MOFs) is placed in chloroform, addition methacrylic anhydride,
Acid binding agent triethylamine is uniformly mixed, and is stirred to react 40~55 hours at 50~70 DEG C, through centrifugation, washing, vacuum drying, is obtained second
The MOFs of alkenyl functionalization；The MOFs of the vinyl functionalization has the following structure formula: metal organic frame-NH-group Q,
Wherein, group Q has structure shown in formula IV:
The structural formula of-2-amino of metal terephthalic acid (TPA) organic frame (MOFs) is as shown in Formulas I or II；
(2) cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation: the MOFs reaction preparation POSS/MOFs for the vinyl functionalization that POSS and step (1) obtain.
According to the present invention, the metal -2- amino terephthalic acid (TPA) organic frame (MOFs) can be obtained by prior art preparation
It arrives.
Central metallic ions M is Zr4+The preparation method of structure MOFs material shown in the Formulas I of ion cluster can refer to document:
Chem.Commun., 2013, described in 49,9449-9451, preparation step is specific as follows: the zirconium chloride of equimolar amounts and 2-ammonia
Base terephthalic acid (TPA) is placed in N, in N-dimethylformamide, is added acetic acid, after ultrasonic disperse, constant temperature 24 hours at 120 DEG C, instead
Product is cooled to room temperature after answering, and is centrifuged out solid, uses N, N-dimethylformamide and chloroform washing respectively
Three to six times, be centrifugally separating to obtain solid, it is vacuum dried to obtain the final product.The zirconium chloride quality and N, N-dimethylformamide matter
Amount is than being 0.05~0.6:15~60；The molar ratio of zirconium chloride, 2-amino terephthalic acid (TPA)s and acetic acid is 1:1:50.
Central metallic ions M is Al3+The preparation method of structure MOFs material shown in the Formulas I of ion cluster can refer to document:
Sep.Purif.Technol.,2013,111,72–81；
Central metallic ions M is Cr3+The preparation method of structure MOFs material shown in the Formulas I of ion cluster can refer to document: RSC
Advances,2012,2,6417–6419；
Central metallic ions M is Fe3+The preparation method of structure MOFs material shown in the Formulas I of ion cluster can refer to document:
Appl.Surf.Sci.,2016,369,130–136；
Central metallic ions M1 is Zn2+The preparation method of structure MOFs material shown in the Formula II of ion cluster can refer to document:
Science,2002,295,469–472。
It is preferred according to the present invention, step (1) metal -2- amino terephthalic acid (TPA) organic frame and chloroform
Mass ratio is 0.2~0.6:20~50；Metal -2- amino terephthalic acid (TPA) organic frame, methacrylic anhydride and triethylamine
Mass ratio is 1:4~8:0.3~0.5.
Preferred according to the present invention, step (1) reaction temperature is 60 DEG C, and the reaction time is 48 hours.
Preferred according to the present invention, step (1) washing is washed five times with chloroform, and the drying is in 50 DEG C
Lower vacuum drying.
Preferred according to the present invention, step (2) the cage modle polysilsesquioxane has structure shown in formula III.
Preferably, when R is vinyl in cage modle polysilsesquioxane (III) structural formula, the poly- sesquialter of eight ethenyl cage models
Siloxanes is reacted with the MOFs's of vinyl functionalization comprising steps of eight ethenyl cage model polysilsesquioxanes and initiator are even
Nitrogen bis-isobutyronitrile is dissolved in organic solvent 1, and the MOFs of vinyl functionalization, ultrasonic disperse is added；Under atmosphere of inert gases, 55
~80 DEG C polymerization reaction 5~16 hours；Then through separation of solid and liquid, wash, be dried to obtain with-NHCOCH (CH3)(CH2)3It is
POSS unit connect the POSS/MOFs hybrid material of bridged bond with MOFs unit.
It is further preferred that the organic solvent 1 is chloroform, tetrahydrofuran or the toluene crossed through Non-aqueous processing；Institute
The mass ratio of the quality and organic solvent 1 of stating eight ethenyl cage model polysilsesquioxanes is 0.1~0.3:10~50.
It is further preferred that the mass ratio of the MOFs of the vinyl functionalization and eight ethenyl cage model polysilsesquioxanes
For 0.3~10:1；Most preferably, the mass ratio of the MOFs of the vinyl functionalization and eight ethenyl cage model polysilsesquioxanes
For 0.3~2:1.
It is further preferred that the quality of the azodiisobutyronitrile and eight ethenyl cage model polysilsesquioxanes and vinyl
The ratio of the MOFs gross mass of functionalization is 0.005~0.03:1；Most preferably, the quality of the azodiisobutyronitrile and eight second
The ratio of the MOFs gross mass of alkenyl cage modle polysilsesquioxane and vinyl functionalization is 0.006~0.015:1.
It is further preferred that the inert gas is nitrogen or argon gas.
Preferably, when R is aminopropyl in cage modle polysilsesquioxane (III) structural formula, the poly- sesquialter of octa-aminopropyl cage type
Siloxanes is reacted with the MOFs's of vinyl functionalization comprising steps of octa-aminopropyl cage type polysilsesquioxane is dissolved in organic
In solvent 2, the MOFs of vinyl functionalization, ultrasonic disperse is added；Under atmosphere of inert gases, 50~80 DEG C of polymerization reactions 10~30
Hour；Through separation of solid and liquid, washing, drying, obtain with-NHCOCH (CH3)CH2NH(CH2)3Connect for POSS unit and MOFs unit
Connect the POSS/MOFs hybrid material of bridged bond.
It is further preferred that the organic solvent 2 is methanol, ethyl alcohol, chloroform or tetrahydrofuran；The octa-aminopropyl
The quality of cage modle polysilsesquioxane and the mass ratio of organic solvent 2 are 0.1~0.3:15~80.
It is further preferred that the mass ratio of the MOFs of the vinyl functionalization and octa-aminopropyl cage type polysilsesquioxane
For 1:0.8~10；Most preferably, the mass ratio of the MOFs Yu octa-aminopropyl cage type polysilsesquioxane of the vinyl functionalization
For 1:1~4.
It is further preferred that the inert gas is nitrogen or argon gas.
Preferably, when R is mercapto propyl in cage modle polysilsesquioxane (III) structural formula, the eight poly- sesquialters of mercapto propyl cage modle
Siloxanes is reacted with the MOFs's of vinyl functionalization comprising steps of by eight mercapto propyl cage modle polysilsesquioxanes and photoinitiator
Benzoin dimethylether is dissolved in organic solvent 3, and the MOFs of vinyl functionalization, ultrasonic disperse is added；Then it is stirred at room temperature
Under, the ultraviolet light of 365nm, 100W 10~40 minutes；Through separation of solid and liquid, washing, drying, obtain with-NHCOCH (CH3)
CH2S(CH2)3The POSS/MOFs hybrid material of bridged bond is connect with MOFs unit for POSS unit.
It is further preferred that the organic solvent 3 is chloroform or tetrahydrofuran；The poly- sesquialter of the eight mercaptos propyl cage modle
The quality of siloxanes and the mass ratio of organic solvent 3 are 0.1~0.3:10~30.
It is further preferred that the mass ratio of the MOFs of the vinyl functionalization and eight mercapto propyl cage modle polysilsesquioxanes
For 1:1~10；Most preferably, the MOFs of the vinyl functionalization and the mass ratio of eight mercapto propyl cage modle polysilsesquioxanes are
1:1~3.
It is further preferred that the quality of the benzoin dimethylether and eight mercapto propyl cage modle polysilsesquioxanes and vinyl
The ratio of the MOFs gross mass of functionalization is 0.01~0.05:1.
Technical characterstic of the invention and the utility model has the advantages that
1, MOFs of the present invention is after the modification of vinyl function monomer, with eight ethenyl cage model polysilsesquioxanes through free radical
Polymerization reaction is prepared with-NHCOCH (CH3)(CH2)3The POSS/MOFs hydridization material of bridged bond is connect with MOFs unit for POSS unit
Material；With octa-aminopropyl cage type polysilsesquioxane through amine-alkene reaction preparation with-NHCOCH (CH3)CH2NH(CH2)3It is mono- for POSS
Member connect the POSS/MOFs hybrid material of bridged bond with MOFs unit；With eight mercapto propyl cage modle polysilsesquioxanes through mercapto-alkene reaction
Preparation is with-NHCOCH (CH3)CH2S(CH2)3The POSS/MOFs hybrid material of bridged bond is connect with MOFs unit for POSS unit.
The invention discloses three kinds of preparation methods, and easy to operate, reaction condition is milder, product yield high, and easily separated and purification.
2, MOFs itself used in the present invention has preferable chemical stability and is easy to carry out functionalization, is conducive to using poly-
Conjunction method prepares cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material；The present invention is by MOFs
It is copolymerized with cage modle polysilsesquioxane molecule, can solve the problems, such as MOFs processing difficulties, be not easy device；And improve material
Thermal stability, mechanical property and processing performance；Cage modle polysilsesquioxane unit improves the deliquescent problem of MOFs.
3, POSS/MOFs hybrid material prepared by the present invention has a variety of pore structures, including cage modle polysilsesquioxane
Pore structure, the pore structure between the pore structure and cage modle polysilsesquioxane and MOFs of MOFs can be poly- by changing cage modle
The mass ratio of silsesquioxane and MOFs regulate and control POSS/MOFs hybrid material and pore structure.Material prepared by the present invention
Material is due to a variety of pore structures, along with the presence of various polarity group in material, so that hybrid material prepared by the present invention
It is had potential application in gas absorption and the fields such as separation, ion and Dye Adsorption, carrier.
6, hybrid material prepared by the present invention is higher than 4.71mg/g to the adsorbance of rhodamine B in rhodamine B aqueous solution,
Adsorption efficiency can reach 97.12%, and reaches the material after adsorption saturation and impregnate 6 hours in N, N-dimethylformamide
The rhodamine B of material absorption is eluted, circulating repetition is reached 7 times or more using number；From the foregoing, it can be seen that prepared by the present invention miscellaneous
Changing material has preferable application effect in Dye Adsorption field, and adsorption effect is good, and reusable.
Detailed description of the invention
Fig. 1 is vinyl functionalization MOFs (metal ion Zr4+Ion cluster) scanning electron microscope diagram.
Fig. 2 is vinyl functionalization MOFs (metal ion Zr4+Ion cluster) N2Absorption-desorption curve and aperture point
Butut.
Fig. 3 is POSS/MOFs hybrid material, vinyl functionalization MOFs (metal ion Zr prepared by embodiment 14+'s
Ion cluster), the XRD spectras of eight ethenyl cage model polysilsesquioxanes.
Fig. 4 is vinyl functionalization MOFs (metal ion Zr4+Ion cluster), embodiment 1 prepare POSS/MOFs it is miscellaneous
P-POSS prepared by change material and comparative example 1 is in rhodamine B solution (15mg/L) to the adsorption effect comparison diagram of rhodamine B.
Specific embodiment
The present invention is described further combined with specific embodiments below, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously, the reagent and material
Material, unless otherwise specified, commercially obtains.
The MOFs of vinyl functionalization is prepared as follows:
Metal ion is Zr4+The preparation method of structure MOFs is referring to document shown in the Formulas I of ion cluster: Chem.Commun.,
Described in 2013,49,9449-9451, specific preparation process is as follows: weighing 93.2mg zirconium chloride, 2-amino of 72.5mg to benzene two
Formic acid, 1.2g acetic acid are placed in 16mLN, in N-dimethylformamide, are put into 200mL high temperature and high pressure kettle after ultrasonic disperse, 120
Constant temperature 24 hours at DEG C, reactant is cooled to room temperature after reaction, is centrifuged out solid, uses N, N-dimethyl methyl respectively
Amide and chloroform wash 4~6 times, are centrifugated out solid, be dried in vacuo at 50 DEG C 12 hours to get.
By in the MOFs merging 20mL chloroform of the above-mentioned preparation of 0.6g, 2.45g methacrylic anhydride and 279.5mg is added
Acid binding agent triethylamine is uniformly mixed, is stirred to react 48 hours at 60 DEG C, is centrifuged out solid, through chloroform washing 3
It is secondary, it is dried in vacuo 8 hours at 50 DEG C, obtains the MOFs of vinyl functionalization.
Fig. 1 is the scanning electron microscope diagram of the vinyl functionalization MOFs of above-mentioned preparation.
Fig. 2 is N of the vinyl functionalization MOFs of above-mentioned preparation under the conditions of 77K2Absorption-desorption curve and pore-size distribution
Figure.As shown in Figure 2, prepared vinyl functionalization MOFs has microcellular structure, and aperture is mainly distributed on 1.2~1.4nm.
Embodiment 1
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
Eight ethenyl cage model polysilsesquioxanes (201.0mg) and initiator azodiisobutyronitrile (3.0mg) are dissolved in
In 20mL anhydrous tetrahydro furan, MOFs (the metal ion Zr of the vinyl functionalization of above-mentioned preparation is added4+Ion cluster)
(202.3mg) and carry out 30 minutes ultrasonic disperses, under nitrogen atmosphere, 60 DEG C polymerization reaction 8 hours, stop reaction, collect solid
Product, it is 12 hours dry at 70 DEG C after washing 3 times with tetrahydrofuran, it obtains with-NHCOCH (CH3)(CH2)3It is mono- for POSS
Member connect the POSS/MOFs hybrid material of bridged bond, yield 95.7% with MOFs unit.
Fig. 3 is the XRD spectra of POSS/MOFs hybrid material manufactured in the present embodiment, it can be seen from the figure that preparation
Without the crystal structure diffraction maximum of cage modle polysilsesquioxane in POSS/MOFs hybrid material, there is the crystal structure diffraction maximum of MOFs,
Illustrate that polymerization reaction has occurred in cage modle polysilsesquioxane and MOFs.
Embodiment 2
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
Eight ethenyl cage model polysilsesquioxanes (211.7mg) and initiator azodiisobutyronitrile (3.8mg) are dissolved in
In the anhydrous chloroform of 30mL, MOFs (the metal ion Zr of the vinyl functionalization of above-mentioned preparation is added4+Ion cluster)
(127.4mg) and ultrasonic disperse 30 minutes, the polymerization reaction 10 hours under the conditions of 65 DEG C, argon gas collected solid after stopping reaction
Product is washed 3 times with chloroform, then 12 hours dry at 70 DEG C, is obtained with-NHCOCH (CH3)(CH2)3It is POSS
Unit connect the POSS/MOFs hybrid material of bridged bond, yield 96.2% with MOFs unit.
Embodiment 3
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
Eight ethenyl cage model polysilsesquioxanes (211.2mg) and initiator azodiisobutyronitrile (2.7mg) are dissolved in
In the anhydrous chloroform of 30mL, MOFs (the metal ion Zr of the vinyl functionalization of above-mentioned preparation is added4+Ion cluster)
(65.0mg) and ultrasonic disperse 20 minutes, under nitrogen atmosphere, 55 DEG C polymerization reaction 12 hours, stop reaction, collect solid product, use
Chloroform washs 3 times, then 12 hours dry at 70 DEG C, obtains with-NHCOCH (CH3)(CH2)3For POSS unit with
MOFs unit connects the POSS/MOFs hybrid material of bridged bond, yield 92.5%.
Embodiment 4
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
Octa-aminopropyl cage type polysilsesquioxane (250.3mg) is dissolved in 50mL chloroform, above-mentioned preparation is added
Vinyl functionalization MOFs (metal ion Zr4+Ion cluster) (125.6mg), after ultrasonic disperse 30 minutes, in nitrogen
Atmosphere polymerization reaction 20 hours at 60 DEG C, stops reaction, collects solid product, dry at 70 DEG C after wash 3 times with chloroform
It dry 12 hours, obtains with-NHCOCH (CH3)CH2NH(CH2)3The POSS/MOFs of bridged bond is connect with MOFs unit for POSS unit
Hybrid material, yield 86.5%.
Embodiment 5
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
Octa-aminopropyl cage type polysilsesquioxane (201.2mg) is dissolved in 30mL tetrahydrofuran, above-mentioned preparation is added
Vinyl functionalization MOFs (metal ion Zr4+Ion cluster) (109.3mg) and ultrasonic disperse 25 minutes；65 DEG C,
Solid product is collected after stopping reaction, with tetrahydrofuran washed product 3 times, then 70 in polymerization reaction 12 hours under argon atmospher
It is 12 hours dry at DEG C, it obtains with-NHCOCH (CH3)CH2NH(CH2)3- for POSS unit with MOFs unit it connect bridged bond
POSS/MOFs hybrid material, yield 85.8%.
Embodiment 6
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
Octa-aminopropyl cage type polysilsesquioxane (200.4mg) is dissolved in 20mL methanol, the second of above-mentioned preparation is added
MOFs (the metal ion Zr of alkenyl functionalization4+Ion cluster) (51.6mg), reactant carry out 20 minutes ultrasounds after, in argon gas
Under atmosphere, 55 DEG C polymerization reaction 24 hours, stop reaction after, the solid product of collection is washed 3 times with chloroform, is then existed
It is 12 hours dry at 70 DEG C, it obtains with-NHCOCH (CH3)CH2NH(CH2)3Bridged bond is connect with MOFs unit for POSS unit
POSS/MOFs hybrid material, yield 89.8%.
Embodiment 7
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
Eight mercapto propyl cage modle polysilsesquioxanes (227.6mg) and photoinitiator benzoin dimethylether (9.0mg) are dissolved
In 30mL tetrahydrofuran, vinyl functionalization MOFs (the metal ion Zr of above-mentioned preparation is added4+Ion cluster)
(112.8mg) and the ultrasonic disperse of progress 25 minutes；Then it is stirred at room temperature, 30 points is irradiated under ultraviolet light (365nm, 100W)
Clock collects solid product, is washed 3 times with tetrahydrofuran, then 12 hours dry at 70 DEG C, obtains with-NHCOCH (CH3)
CH2S(CH2)3The POSS/MOFs hybrid material of bridged bond is connect with MOFs unit for POSS unit.Yield is 88.7%.
Embodiment 8
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
Eight mercapto propyl cage modle polysilsesquioxanes (219.6mg) and photoinitiator benzoin dimethylether (8.6mg) are dissolved
In 20mL chloroform, vinyl functionalization MOFs (the metal ion Zr of above-mentioned preparation is added4+Ion cluster)
(100.2mg) is stirred at room temperature after reactant ultrasonic disperse 25 minutes, and 25 points are irradiated under ultraviolet light (365nm, 100W)
Clock, it is 12 hours dry at 70 DEG C after the solid product of collection washs 3 times with chloroform, it obtains with-NHCOCH (CH3)CH2S
(CH2)3The POSS/MOFs hybrid material of bridged bond, yield 88.3% are connect with MOFs unit for POSS unit.
Embodiment 9
A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs)
Preparation method, comprising steps of
Eight mercapto propyl cage modle polysilsesquioxanes (220.5mg) and photoinitiator benzoin dimethylether (8.4mg) are dissolved
In 25mL tetrahydrofuran, vinyl functionalization MOFs (the metal ion Zr of above-mentioned preparation is added4+Ion cluster)
(85.4mg) carries out 20 minutes ultrasonic disperses afterwards, is then stirred at room temperature, irradiating ultraviolet light (365nm, 100W) 20 minutes
After collect solid product, wash 3 times with tetrahydrofuran, it is then 12 hours dry at 70 DEG C, obtain with-NHCOCH (CH3)CH2S
(CH2)3The POSS/MOFs hybrid material of bridged bond, yield 86.9% are connect with MOFs unit for POSS unit.
Comparative example 1
Eight ethenyl cage model polysilsesquioxanes (300.3mg) and initiator azodiisobutyronitrile (2.3mg) are dissolved in
In 20mL anhydrous tetrahydro furan, under nitrogen atmosphere, 65 DEG C polymerization reaction 12 hours, stop reaction, collect solid product, with tetrahydro furan
It is 12 hours dry at 70 DEG C after muttering washing 3 times, obtain the autopolymer (p-POSS) of eight ethenyl cage model polysilsesquioxanes.It produces
Rate is 88.2%.
Test example 1
Vinyl functionalization MOFs (the metal ion Zr of the above-mentioned preparation of 10mg is weighed respectively4+Ion cluster), embodiment 1
The p-POSS of POSS/MOFs and comparative example 1 preparation of preparation, and it is respectively placed in the rhodamine B solution that 3mL concentration is 15mg/L
In, it vibrates 24 hours at room temperature, passes through the extinction of remaining rhodamine B in solution after ultraviolet-visible absorption spectrum detection absorption
Degree.
Fig. 4 is vinyl functionalization MOFs (metal ion Zr4+Ion cluster), embodiment 1 prepare POSS/MOFs and
P-POSS prepared by comparative example 1 is to the adsorption effect figure of rhodamine B, by can be calculated, vinyl functionalization MOFs (metal ion
For Zr4+Ion cluster), the adsorbance point of p-POSS prepared by POSS/MOFs and comparative example 1 prepared by embodiment 1 to rhodamine B
Not Wei 2.25mg/g, 4.71mg/g and 1.10mg/g, adsorption efficiency is respectively 46.39%, 97.12% and 22.22%.The present invention
POSS/MOFs prepared by embodiment 1 is in the rhodamine B solution of 15mg/L after adsorption saturation, in N, N-dimethylformamide
The rhodamine B that can elute material absorption for 6 hours is impregnated, circulating repetition utilizes 7 times, and adsorption efficiency still can reach
78.95%；It can be seen from the above, hybrid material prepared by the present invention has preferable application effect, absorption in Dye Adsorption field
Effect is good, and reusable.
Claims (10)
1. a kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs),
It is characterized in that, the hybrid material is figure reticular structure, include such as flowering structure: metal organic frame-NH in molecular structure2's
The structural unit of structural unit grafting cage modle polysilsesquioxane；Metal organic frame-the NH2It is metal -2- amino to benzene
Dioctyl phthalate organic frame has structure shown in Formulas I or II；
Wherein, in Formulas I structural formula, M Al3+Ion cluster, Fe3+Ion cluster, Zr4+Ion cluster or Cr3+Ion cluster,Represent ligand 2-amino terephthalic acid (TPA)；In Formula II structural formula, M1 Zn2+Ion cluster,Represent ligand 2-
Amino terephthalic acid (TPA)；
The cage modle polysilsesquioxane has structure shown in following formula III:
Wherein, in formula III structural formula, R is vinyl, aminopropyl or mercapto propyl；
When the R of cage modle polysilsesquioxane is vinyl, the metal organic frame-NH2Structural unit and the poly- sesquialter of cage modle
The connection bridged bond of the structural unit of siloxanes is-NHCOCH (CH3)(CH2)3–；When the R of cage modle polysilsesquioxane is aminopropyl
When, the metal organic frame-NH2Structural unit and cage modle polysilsesquioxane structural unit connection bridged bond be-
NHCOCH(CH3)CH2NH(CH2)3–；When the R of cage modle polysilsesquioxane is mercapto propyl, the metal organic frame-NH2's
The connection bridged bond of the structural unit of structural unit and cage modle polysilsesquioxane is-NHCOCH (CH3)CH2S(CH2)3–。
2. cage modle polysilsesquioxane as described in claim 1/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material
(POSS/MOFs) preparation method, comprising steps of
(1) preparation of the MOFs of vinyl functionalization；
Metal -2- amino terephthalic acid (TPA) organic frame (MOFs) is placed in chloroform, methacrylic anhydride is added, ties up acid
Agent triethylamine is uniformly mixed, and is stirred to react 40~55 hours at 50~70 DEG C, through centrifugation, washing, vacuum drying, is obtained vinyl
The MOFs of functionalization；The MOFs of the vinyl functionalization has the following structure formula: metal organic frame-NH-group Q, wherein
Group Q has structure shown in formula IV:
The structural formula of the metal -2- amino terephthalic acid (TPA) organic frame (MOFs) is as shown in Formulas I or II；
(2) cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material (POSS/MOFs) system
It is standby: the MOFs reaction preparation POSS/MOFs for the vinyl functionalization that POSS and step (1) obtain.
3. cage modle polysilsesquioxane according to claim 2/metal -2- amino terephthalic acid (TPA) organic frame hydridization material
Expect the preparation method of (POSS/MOFs), which is characterized in that in step (1), including one or more in the following conditions:
A, the mass ratio of the metal -2- amino terephthalic acid (TPA) organic frame and chloroform is 0.2~0.6:20~50；Gold
The mass ratio of category -2- amino terephthalic acid (TPA) organic frame, methacrylic anhydride and triethylamine is 1:4~8:0.3~0.5；
B, the reaction temperature is 60 DEG C, and the reaction time is 48 hours.
4. cage modle polysilsesquioxane according to claim 2/metal -2- amino terephthalic acid (TPA) organic frame hydridization material
Expect the preparation method of (POSS/MOFs), which is characterized in that step (2) the cage modle polysilsesquioxane has knot shown in formula III
Structure.
5. cage modle polysilsesquioxane according to claim 4/metal -2- amino terephthalic acid (TPA) organic frame hydridization material
Expect the preparation method of (POSS/MOFs), which is characterized in that in step (2), as R in cage modle polysilsesquioxane (III) structural formula
When for vinyl, eight ethenyl cage model polysilsesquioxanes are reacted with the MOFs's of vinyl functionalization comprising steps of by eight second
Alkenyl cage modle polysilsesquioxane and initiator azodiisobutyronitrile are dissolved in organic solvent 1, and vinyl functionalization is added
MOFs, ultrasonic disperse；Under atmosphere of inert gases, 55~80 DEG C polymerization reaction 5~16 hours；Then through separation of solid and liquid, washing, dry
It is dry to obtain with-NHCOCH (CH3)(CH2)3The POSS/MOFs of bridged bond is connected for the structural unit of POSS and the structural unit of MOFs
Hybrid material.
6. cage modle polysilsesquioxane according to claim 5/metal -2- amino terephthalic acid (TPA) organic frame hydridization material
Expect the preparation method of (POSS/MOFs), which is characterized in that including one or more in the following conditions:
A, the organic solvent 1 is chloroform, tetrahydrofuran or the toluene crossed through Non-aqueous processing；Eight ethenyl cage model is poly-
The quality of silsesquioxane and the mass ratio of organic solvent 1 are 0.1~0.3:10~50；
B, the mass ratio of the MOFs of the vinyl functionalization and eight ethenyl cage model polysilsesquioxanes is 0.3~10:1；Most
Preferably, the mass ratio of the MOFs of the vinyl functionalization and eight ethenyl cage model polysilsesquioxanes is 0.3~2:1；
C, the quality of the azodiisobutyronitrile and the MOFs of eight ethenyl cage model polysilsesquioxanes and vinyl functionalization are total
The ratio of quality is 0.005~0.03:1；Most preferably, the quality of the azodiisobutyronitrile and the poly- sesquialter of eight ethenyl cage models
The ratio of the MOFs gross mass of siloxanes and vinyl functionalization is 0.006~0.015:1.
7. cage modle polysilsesquioxane according to claim 4/metal -2- amino terephthalic acid (TPA) organic frame hydridization material
Expect the preparation method of (POSS/MOFs), which is characterized in that in step (2), as R in cage modle polysilsesquioxane (III) structural formula
When for aminopropyl, octa-aminopropyl cage type polysilsesquioxane is reacted with the MOFs's of vinyl functionalization comprising steps of by eight ammonia
Propyl cage modle polysilsesquioxane is dissolved in organic solvent 2, and the MOFs of vinyl functionalization, ultrasonic disperse is added；Indifferent gas
Under body atmosphere, 50~80 DEG C polymerization reaction 10~30 hours；Through separation of solid and liquid, washing, drying, obtain with-NHCOCH (CH3)
CH2NH(CH2)3The POSS/MOFs hybrid material of bridged bond is connected for the structural unit of POSS and the structural unit of MOFs.
8. cage modle polysilsesquioxane according to claim 7/metal -2- amino terephthalic acid (TPA) organic frame hydridization material
Expect the preparation method of (POSS/MOFs), which is characterized in that including one or more in the following conditions:
A, the organic solvent 2 is methanol, ethyl alcohol, chloroform or tetrahydrofuran；The poly- silsesquioxane of octa-aminopropyl cage type
The quality of alkane and the mass ratio of organic solvent 2 are 0.1~0.3:15~80；
B, the mass ratio of the MOFs Yu octa-aminopropyl cage type polysilsesquioxane of the vinyl functionalization are 1:0.8~10；Most
Preferably, the mass ratio of the MOFs Yu octa-aminopropyl cage type polysilsesquioxane of the vinyl functionalization are 1:1~4.
9. cage modle polysilsesquioxane according to claim 4/metal -2- amino terephthalic acid (TPA) organic frame hydridization material
Expect the preparation method of (POSS/MOFs), which is characterized in that in step (2), as R in cage modle polysilsesquioxane (III) structural formula
When for mercapto propyl, eight mercapto propyl cage modle polysilsesquioxanes are reacted with the MOFs's of vinyl functionalization comprising steps of by eight mercaptos
Propyl cage modle polysilsesquioxane and photoinitiator benzoin dimethylether are dissolved in organic solvent 3, and vinyl functionalization is added
MOFs, ultrasonic disperse；Then under stirring at room temperature, the ultraviolet light of 365nm, 100W 10~40 minutes；Be separated by solid-liquid separation,
Washing, drying, obtain with-NHCOCH (CH3)CH2S(CH2)3For the structural unit of POSS and the structural unit connecting bridge of MOFs
The POSS/MOFs hybrid material of key.
10. cage modle polysilsesquioxane according to claim 9/metal -2- amino terephthalic acid (TPA) organic frame hydridization
The preparation method of material (POSS/MOFs), which is characterized in that including one or more in the following conditions:
A, the organic solvent 3 is chloroform or tetrahydrofuran；The quality of the eight mercaptos propyl cage modle polysilsesquioxane and
The mass ratio of organic solvent 3 is 0.1~0.3:10~30；
B, the mass ratio of the MOFs of the vinyl functionalization and eight mercapto propyl cage modle polysilsesquioxanes is 1:1~10；It is optimal
Choosing, the mass ratio of the MOFs of the vinyl functionalization and eight mercapto propyl cage modle polysilsesquioxanes is 1:1~3；
C, the quality of the benzoin dimethylether and the MOFs of eight mercapto propyl cage modle polysilsesquioxanes and vinyl functionalization are total
The ratio of quality is 0.01~0.05:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811322806.7A CN109400903B (en) | 2018-11-08 | 2018-11-08 | Cage-type polysilsesquioxane/metal-2-amino terephthalic acid organic framework hybrid material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811322806.7A CN109400903B (en) | 2018-11-08 | 2018-11-08 | Cage-type polysilsesquioxane/metal-2-amino terephthalic acid organic framework hybrid material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109400903A true CN109400903A (en) | 2019-03-01 |
| CN109400903B CN109400903B (en) | 2020-05-22 |
Family
ID=65472404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811322806.7A Active CN109400903B (en) | 2018-11-08 | 2018-11-08 | Cage-type polysilsesquioxane/metal-2-amino terephthalic acid organic framework hybrid material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109400903B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100303A (en) * | 2019-12-02 | 2020-05-05 | 厦门大学 | Preparation method and application of organic phosphine grafted hollow metal organic framework material |
| CN113045762A (en) * | 2021-03-03 | 2021-06-29 | 中国安全生产科学研究院 | Modified MOFs flame retardant and preparation method and application thereof |
| CN113559828A (en) * | 2021-07-30 | 2021-10-29 | 中国农业科学院农业质量标准与检测技术研究所 | Polyacrylic acid magnetic nano composite material, preparation method and application |
| CN116102820A (en) * | 2022-12-23 | 2023-05-12 | 理工清科(重庆)先进材料研究院有限公司 | Metal-MPOFs/polymer composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845138A (en) * | 2010-04-01 | 2010-09-29 | 浙江大学宁波理工学院 | Method for preparing degradable organic-inorganic nanometer hybrid material containing POSS (Polyhedral Oligomeric Silsesquioxanes) |
| CN102643304A (en) * | 2012-03-30 | 2012-08-22 | 山东大学 | Preparation method of cage poly (phenylsilsequioxane) |
| CN106062079A (en) * | 2014-03-07 | 2016-10-26 | 株式会社东进世美肯 | Thermoplastic resin composition comprising silsesquioxane composite polymer |
-
2018
- 2018-11-08 CN CN201811322806.7A patent/CN109400903B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845138A (en) * | 2010-04-01 | 2010-09-29 | 浙江大学宁波理工学院 | Method for preparing degradable organic-inorganic nanometer hybrid material containing POSS (Polyhedral Oligomeric Silsesquioxanes) |
| CN102643304A (en) * | 2012-03-30 | 2012-08-22 | 山东大学 | Preparation method of cage poly (phenylsilsequioxane) |
| CN106062079A (en) * | 2014-03-07 | 2016-10-26 | 株式会社东进世美肯 | Thermoplastic resin composition comprising silsesquioxane composite polymer |
Non-Patent Citations (2)
| Title |
|---|
| AMOL DESHMUKH,CHENG-CHAU CHIU,YUN-WEN CHEN,ET.AL: "Tunable Gravimetric and Volumetric Hydrogen Storage Capacities in", 《ACS APPL. MATER. INTERFACES》 * |
| SANIL ES,CHO KH, ET.AL: "A polyhedral oligomeric silsesquioxane functionalized copper trimesate", 《CHEMICAL COMMUNICATIONS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100303A (en) * | 2019-12-02 | 2020-05-05 | 厦门大学 | Preparation method and application of organic phosphine grafted hollow metal organic framework material |
| WO2021109993A1 (en) * | 2019-12-02 | 2021-06-10 | 厦门大学 | Preparation method for organic phosphine grafted hollow metal organic framework material and use thereof |
| CN113045762A (en) * | 2021-03-03 | 2021-06-29 | 中国安全生产科学研究院 | Modified MOFs flame retardant and preparation method and application thereof |
| CN113559828A (en) * | 2021-07-30 | 2021-10-29 | 中国农业科学院农业质量标准与检测技术研究所 | Polyacrylic acid magnetic nano composite material, preparation method and application |
| CN113559828B (en) * | 2021-07-30 | 2023-05-26 | 中国农业科学院农业质量标准与检测技术研究所 | Polyacrylic acid magnetic nanocomposite, preparation method and application |
| CN116102820A (en) * | 2022-12-23 | 2023-05-12 | 理工清科(重庆)先进材料研究院有限公司 | Metal-MPOFs/polymer composite material and preparation method and application thereof |
| CN116102820B (en) * | 2022-12-23 | 2024-06-14 | 理工清科(重庆)先进材料研究院有限公司 | Metal-MPOFs/polymer composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109400903B (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109400903A (en) | A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material and preparation method thereof | |
| CN104710559B (en) | A kind of method preparing metal-organic framework materials thin film | |
| Satheeshkumar et al. | Thiol–ene photopolymerization of vinyl-functionalized metal–organic frameworks towards mixed-matrix membranes | |
| CN105694051A (en) | Click chemistry based metal-organic framework cross-linking membrane and preparation method and application thereof | |
| CN109970912B (en) | Preparation method of flavonoid magnetic molecularly imprinted polymer | |
| CN109880294A (en) | A kind of epoxy nano composite material of tannic acid modified graphene oxide | |
| Türkmen et al. | Poly (hydroxyethyl methacrylate) nanobeads containing imidazole groups for removal of Cu (II) ions | |
| CN113751076B (en) | Bis-imidazolium palladium-supported porous organic polymer catalyst and preparation method and application thereof | |
| CN107353372B (en) | A kind of preparation method of the nNOS-PSD-95 uncoupler imprint surface polymer based on magnetic mesoporous molecular sieve | |
| CN113522244A (en) | Covalent organic framework composite material and preparation method and application thereof | |
| CN107999019B (en) | Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof | |
| CN113567594B (en) | Detection method of norfloxacin based on MOFs type molecularly imprinted polymer | |
| CN110327792A (en) | A kind of mixed substrate membrane containing nano-grade molecular sieve of tree and its preparation method and application of bi-component nanometer additive building | |
| CN105294957A (en) | Method for preparing high-aldehyde content polymer microspheres on basis of lignin | |
| CN106977746A (en) | Ultrabranching polyamide or derivatives thereof mesoporous molecular sieve composite material, its preparation method and application | |
| CN111909311A (en) | Zearalenone functionalized graphene surface molecularly imprinted material and preparation method thereof | |
| CN104959116A (en) | MOFs (metal-organic frameworks) pulp fiber composite and forming and preparing method thereof | |
| CN113929840B (en) | Hollow porous medium for separating and enriching taxane, preparation and application thereof | |
| CN104744617B (en) | Five yuan of melon ring bridging acrylate copolymer microballoons and preparation method and application | |
| CN115212856A (en) | Preparation and application of surface polymer functionalized spherical metal organic framework material | |
| CN110172158B (en) | Preparation method of hierarchical porous metal organic framework material MIL-101(Cr) | |
| CN114950147A (en) | For CO 2 Separated Trnano's Base type polyimide hybrid membrane and preparation method thereof | |
| CN115228426A (en) | Modified silicon dioxide adsorbent for trapping medium-low concentration carbon dioxide | |
| CN110156941B (en) | Preparation method of patulin magnetic molecularly imprinted polymer | |
| CN107417954B (en) | Ibuprofen imprinted composite membrane initiated by surface grafting atom transfer radical polymerization and preparation method and application thereof |
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 |