CN106317278B - A kind of preparation method of monodisperse nucleocapsid ZIF-8@PDVB-VI complex microspheres - Google Patents
A kind of preparation method of monodisperse nucleocapsid ZIF-8@PDVB-VI complex microspheres Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of 8@PDVB VI complex microspheres of monodisperse nucleocapsid ZIF.For the 8@PDVB complex microspheres of monodisperse nucleocapsid ZIF with the poly- divinyl of functionalization monodisperse (PDVB VI) for core, the claddings of ZIF 8 are grown on the surfaces PDVB VI.For the grain size of the monodisperse Core-shell structure material at 1 10 μm, the outer casing thickness is 10 100nm.The preparation method of the present invention is to first pass through primary sedimentation polymerization to prepare monodispersed high crosslinking PDVB microballoons, it polymerize to obtain the PDVB VI microballoons of 1 vinyl imidazole functionalization of surface by secondary precipitation on this basis, the ZIF 8 that single-layer or multi-layer is finally carried out on the surfaces PDVB VI is coated.Preparation method provided by the invention is simple and reliable, of low cost, and equipment is simple, and monodispersity and being evenly coated property are good.
Description
Technical field
The present invention relates to a kind of preparation methods of monodisperse nucleocapsid ZIF-8@PDVB-VI complex microspheres, belong to novel
Hybrid inorganic-organic materials preparation field.
Background technology
Metal-organic framework (Metal organic frameworks, MOFs) is led to by metal ion and organic ligand
The crystalline material with periodic network structure made of self assembly ligand complex is crossed, is quickly grown in recent years.MOFs have than
Surface is big, porosity is high, skeleton structure can reconcile channel surfaces the features such as can modifying, gas storage and separation, heterogeneous catalysis,
All there is great application potential in molecular recognition, separation and sensing etc..However, the mechanical strength due to MOFs is low, size
The defects of small, makes it be subject to certain restrictions in the application in the fields such as heterogeneous catalysis and separation.MOFs materials are coated on height
The substrate material surface of mechanical strength and thermal stability can obtain novel organic and inorganic multifunctional composite, make up it
Defect.
Zeolitic imidazolate framework material (Zeoliticimidazolate frameworks, ZIFs) is by zinc or cobalt etc.
The coordination polymer that transition metal ions is formed with the nitrogen-atoms Coordinate self-assembly in imidazoles or imdazole derivatives, is MOFs materials
A Main Branches.ZIFs has the property of similar zeolite, compared to most of MIFs materials have higher thermal stability and
Chemical stability is stored and is detached in gas, and the fields such as catalysis have good application prospect.
Organic polymer has higher mechanical strength and thermal stability and excellent chemical stability, is to prepare again
The excellent carrier of condensation material.The polydivinylbenezene microballoon prepared using precipitation polymerization process also has microspherulite diameter controllable, single
Good dispersion prepares the advantages that simple.The hybrid inorganic-organic nucleocapsid that MOFs is prepared using polydivinylbenezene microballoon as carrier is micro-
Ball has not been reported.
Invention content
The object of the present invention is to provide a kind of preparation methods of monodisperse nucleocapsid ZIF-8@PDVB-VI complex microspheres
To achieve the above object, the technical solution adopted by the present invention is：
(1) by divinylbenzene, initiator and reaction medium mixing, primary sedimentation pre-polymer solution is obtained, formula is as follows：
Divinylbenzene volume is 1-5%v, and v is reaction medium volume herein, and initiator quality 0.5-25%w, w is diethyl herein
The quality of alkenyl benzene；Primary sedimentation pre-polymer solution ultrasound is deaerated, is sealed after logical nitrogen deoxygenation, in constant temperature water bath oscillating condition
Lower progress primary sedimentation polymerisation is dried after products therefrom washing to get to the poly- divinylbenzene microspheres of monodisperse；
(2) poly- divinylbenzene microspheres obtained by step (1) and 1- vinyl imidazoles and initiator are evenly spread to instead together
It answers in medium, obtains secondary precipitation pre-polymer solution, formula is as follows：Poly- divinylbenzene microspheres quality is 0.02-10%w1, herein
w1For reaction medium quality, 1- vinyl imidazole quality is 0.01-1%v1, v1For reaction medium volume, initiator quality is
0.5-25%w2, w herein2For the quality of 1- vinyl imidazoles；Secondary precipitation pre-polymer solution ultrasound is deaerated, nitrogen deoxygenation is led to
After seal, under constant temperature water bath oscillating condition, carry out secondary precipitation polymerisation；It is dried to get to 1- after products therefrom washing
Vinyl imidazole functional poly divinylbenzene microspheres (PDVB-VI)；
(3) by obtained by step (2) 1- vinyl imidazole functional poly divinylbenzene microspheres and zinc nitrate hexahydrate it is uniform
It is dispersed in reaction medium, room-temperature water bath oscillation reaches balance, obtains uniform mixture, oscillation is kept, by 2- methyl
Imidazoles is dispersed in reaction medium and pours into said mixture, continues oscillating reactions, detaches solid production after reaction
Object obtains once coating ZIF-8@PDVB-VI nucleocapsid microballoons；The reaction medium dosage phase used twice in above-mentioned steps
Deng functional poly divinylbenzene microspheres：Zinc nitrate hexahydrate：2-methylimidazole：The mass ratio of reaction medium total amount is twice
0.01-1：0.5：1-10：10-100.
The primary cladding poly- divinylbenzene of ZIF-8@PDVB-VI nucleocapsid microballoon replacement functionizations obtained by step (3) is micro-
Ball repeat step (3) operation is primary secondary or multiple difference can obtain secondary or three times or multiple cladding ZIF-8@PDVB-VI
Nucleocapsid microballoon.
The initiator is azodiisobutyronitrile (AIBN)；Reaction medium is second described in step (1) or step (2)
The mixture of nitrile or acetonitrile and toluene；Reaction medium described in step (3) is methanol or one kind in water or two kinds；The ultrasound
The time of degassing operation is 5-15min, and the time for leading to nitrogen deoxygenation operation is 5-15min.
The primary sedimentation polymerisation and secondary precipitation polymerisation carry out in water-bath constant temperature oscillator, reaction temperature
Degree is 50-70 DEG C, and the reaction time is 12-24h；The concussion frequency of primary sedimentation polymerisation is in 0-2h in step (1)
0-80rpm is kept, frequency of oscillation is maintained at 120-160rpm until primary sedimentation polymerisation terminates later；Two in step (2)
Frequency is shaken in secondary precipitation polymerization reaction process remains at 120-160rpm；Step (3) is reacted in water-bath constant temperature oscillator
Middle progress, concussion frequency is 120-160rpm, reaction time 0.2-2h in reaction process.
Washing operation described in step (1) or step (2) is that acetonitrile and acetone is used to wash successively, 50-70 DEG C after washing
It is dried in vacuo 12-24h.
Functionalization monomer used in step (2) is 1- vinyl imidazoles.
Described in step (3) detach solid product the specific steps are：Product centrifuges 5- with rate 1000-3000rpm
15min is discarded supernatant, and is centrifuged again after adding methanol to be resuspended, and repeats aforesaid operations 3-5 times.
Monodisperse nucleocapsid ZIF-8@PDVB-VI complex microspheres, can prepare according to the following steps：
(1) by divinylbenzene, initiator and reaction medium mixing, primary sedimentation pre-polymer solution is obtained, formula is as follows：
Divinylbenzene volume is 1-5%v, and v is reaction medium volume herein, and initiator quality 0.5-25%w, w is diethyl herein
The quality of alkenyl benzene；Primary sedimentation pre-polymer solution ultrasound is deaerated, is sealed after logical nitrogen deoxygenation, in constant temperature water bath oscillating condition
Lower progress primary sedimentation polymerisation is dried after products therefrom washing to get to the poly- divinylbenzene microspheres of monodisperse；
(2) poly- divinylbenzene microspheres obtained by step (1) and 1- vinyl imidazoles and initiator are evenly spread to instead together
It answers in medium, obtains secondary precipitation pre-polymer solution, formula is as follows：Poly- divinylbenzene microspheres quality is 0.02-10%w1, herein
w1For reaction medium quality, 1- vinyl imidazole quality is 0.01-1%v1, v1For reaction medium volume, initiator quality is
0.5-25%w2, w herein2For the quality of 1- vinyl imidazoles；Secondary precipitation pre-polymer solution ultrasound is deaerated, nitrogen deoxygenation is led to
After seal, under constant temperature water bath oscillating condition, carry out secondary precipitation polymerisation；It is dried to get to 1- after products therefrom washing
Vinyl imidazole functional poly divinylbenzene microspheres (PDVB-VI)；
(3) by obtained by step (2) 1- vinyl imidazole functional poly divinylbenzene microspheres and zinc nitrate hexahydrate it is uniform
It is dispersed in reaction medium, room-temperature water bath oscillation reaches balance, obtains uniform mixture, oscillation is kept, by 2- methyl
Imidazoles is dispersed in reaction medium and pours into said mixture, continues oscillating reactions, detaches solid production after reaction
Object obtains once coating ZIF-8@PDVB-VI nucleocapsid microballoons；The reaction medium dosage phase used twice in above-mentioned steps
Deng functional poly divinylbenzene microspheres：Zinc nitrate hexahydrate：2-methylimidazole：The mass ratio of reaction medium total amount is twice
0.01-1：0.5：1-10：10-100；
It is an advantage of the invention that：Preparation method is simple and reliable, of low cost, and equipment is simple, monodispersity and is evenly coated
Property is good.
The monodisperse nucleocapsid ZIF-8@PDVB-VI complex microspheres that the present invention obtains can be by coating number control
The load capacity of ZIF-8.
Description of the drawings
Fig. 1 is the SEM figures of PDVB carriers in embodiment 1；(a) amplify 2000 times, (b) amplify 5000 times.
Fig. 2 is the SEM figures of PDVB-VI functional supports in embodiment 1；(a) amplify 5000 times, (b) amplify 15000 times.
Fig. 3 is the SEM figures that ZIF-8@PDVB-VI are once coated in embodiment 1；(a) amplify 2000 times, (b) amplify 4000
Times, (c) amplify 16000 times, (d) amplifies 200000 times.
Fig. 4 is the TEM figures that ZIF-8@PDVB-VI are once coated in embodiment 1.
Fig. 5 is the SEM figures of secondary cladding ZIF-8@PDVB-VI in embodiment 2.
Specific implementation mode
Embodiment 1
0.6mL divinylbenzenes and 0.0545gAIBN are dissolved into round-bottomed flask in 30mL acetonitriles and once sunk
Shallow lake pre-polymer solution.Primary sedimentation pre-polymer solution ultrasound 10min, logical nitrogen 15min are sealed after removing oxygen molecule, then will
The round-bottomed flask being sealed is put into water bath chader, is at the uniform velocity warming up to 60 DEG C from room temperature in 1.5h, frequency 0- is shaken in water-bath
2h keeps 0rpm, and 140rpm is risen to after 2h, and precipitation polymerization reacts for 24 hours.The white product of generation uses acetonitrile and acetone to wash successively
It washs, removes residual monomer and interfering substance, be placed in vacuum drying chamber dry for 24 hours to get to the poly- divinyl of monodisperse in 60 DEG C
Benzene microballoon (PDVB), as shown in Figure 1.It can be seen that from FIG. 1 a that spherical regular, no coalescence of PDVB, and there is good grain
Diameter monodispersity.As can be seen that PDVB microsphere features smooth surfaces, grain size is about 4.8 μm from Fig. 1 b.
The poly- divinylbenzene microspheres 200mg of gained monodisperse and 38.1 μ L1- vinyl imidazoles function monomers and 22mg are caused
Agent AIBN is evenly spread to together obtains secondary precipitation pre-polymer solution in 30mL acetonitriles, secondary precipitation pre-polymer solution ultrasound is taken off
It is sealed after gas 10min, logical nitrogen 15min, the secondary precipitation pre-polymer solution of sealing is put into 60 DEG C of water-bath constant temperature oscillators
For 24 hours, water-bath frequency of oscillation is maintained at 140rpm for reaction.The faint yellow product generated uses acetonitrile and acetone to wash successively, removal
Residual monomer and interfering substance are placed in vacuum drying chamber dry for 24 hours to get to functional poly divinylbenzene microspheres in 60 DEG C
(PDVB-VI), as shown in Figure 2.As can be seen that PDVB-VI does not have significant change relative to PDVB microspherulite diameters from Fig. 2 a.From
As can be seen that 1- vinyl imidazoles function monomer forms many equally distributed small agglomerates on the surfaces PDVB in Fig. 2 b.
40mL methanol is added in gained functional poly divinylbenzene microspheres 50mg together with 0.5866g zinc nitrate hexahydrates
In, 30min is vibrated after ultrasonic disperse 5min in room-temperature water bath, frequency of oscillation 150rpm makes Zn ions and the surfaces PDVB-VI
Imidazole group up to coordination be saturated.Another 40mL methanol dissolved with 1.2980g 2-methylimidazoles is quickly poured into above-mentioned molten
In liquid, after persistent oscillation 60min, frequency of oscillation 150rpm.Products therefrom is centrifuged into 5min with rate 2000rpm, is discarded supernatant,
It is centrifuged again after adding methanol to be resuspended, repeats aforesaid operations 3 times.Finally, it obtains once coating ZIF-8@PDVB-VI microballoons, such as Fig. 3
Shown in 4.As can be seen that nanometer ZIF-8 forms uniform packet in all PDVB-VI microsphere surfaces from Fig. 3 a, 3b and 3c
It covers, clad ratio is close to the surfaces 100%, PDVB-VI without apparent exposed.As can be seen that the size of ZIF-8 nano particles from Fig. 3 d
About 20nm, tight coating, without clear gap between particle.Thickness by the TEM graph discovery clads of Fig. 4 is about 20nm,
Therefore further conclude that primary cladding is that single layer coats.
Embodiment 2
0.6mL divinylbenzenes and 0.0545gAIBN are dissolved into round-bottomed flask in 30mL acetonitriles and once sunk
Shallow lake pre-polymer solution.Primary sedimentation pre-polymer solution ultrasound 10min, logical nitrogen 15min are sealed after removing oxygen molecule, then will
The round-bottomed flask being sealed is put into constant temperature oscillation water-bath, is at the uniform velocity warming up to 60 DEG C from room temperature in 1.5h, frequency is shaken in water-bath
0-2h keeps 0rpm, and 140rpm is risen to after 2h, and precipitation polymerization reacts for 24 hours.The white product of generation uses acetonitrile and acetone successively
Washing removes residual monomer and interfering substance, is placed in vacuum drying chamber dry for 24 hours to get to the poly- diethyl of monodisperse in 60 DEG C
Alkene benzene microballoon (PDVB), as shown in Figure 1.It can be seen that from FIG. 1 a that spherical regular, no coalescence of PDVB, and with good
Grain size monodispersity.As can be seen that PDVB microsphere features smooth surfaces, grain size is about 4.8 μm from Fig. 1 b.
The poly- divinylbenzene microspheres 200mg of gained monodisperse and 38.1 μ L 1- vinyl imidazoles function monomers and 22mg are drawn
Hair agent AIBN is evenly spread to together obtains secondary precipitation pre-polymer solution in 30mL acetonitriles, by secondary precipitation pre-polymer solution ultrasound
Deaerate 10min, is sealed after logical nitrogen 15min, the secondary precipitation pre-polymer solution of sealing is put into 60 DEG C of water-bath constant temperature oscillators
For 24 hours, water-bath frequency of oscillation is maintained at 140rpm for middle reaction.The faint yellow product generated uses acetonitrile and acetone to wash successively, goes
Except residual monomer and interfering substance, it is placed in vacuum drying chamber dry for 24 hours to get to functional poly divinylbenzene microspheres in 60 DEG C
(PDVB-VI), as shown in Figure 2.As can be seen that PDVB-VI does not have significant change relative to PDVB microspherulite diameters from Fig. 2 a.From
As can be seen that 1- vinyl imidazoles function monomer forms many equally distributed small agglomerates on the surfaces PDVB in Fig. 2 b.
40mL methanol is added in gained functional poly divinylbenzene microspheres 50mg together with 0.5866g zinc nitrate hexahydrates
In, 30min is vibrated after ultrasonic disperse 5min in room-temperature water bath, frequency of oscillation 150rpm makes Zn ions and the surfaces PDVB-VI
Imidazole group up to coordination be saturated.Another 40mL methanol dissolved with 1.2980g 2-methylimidazoles is quickly poured into above-mentioned molten
In liquid, after persistent oscillation 60min, frequency of oscillation 150rpm.Products therefrom is centrifuged into 5min with rate 2000rpm, is discarded supernatant,
It is centrifuged again after adding methanol to be resuspended, repeats aforesaid operations 3 times.Finally, it obtains once coating ZIF-8@PDVB-VI, such as Fig. 3 and 4
It is shown.As can be seen that nanometer ZIF-8 forms uniform cladding in all PDVB-VI microsphere surfaces from Fig. 3 a, 3b and 3c,
Clad ratio is close to the surfaces 100%, PDVB-VI without apparent exposed.The size of ZIF-8 nano particles is can be seen that from Fig. 3 d about
For 20nm, tight coating, without clear gap between particle.Thickness by the TEM graph discovery clads of Fig. 4 is about 20nm, because
This further concludes that primary cladding is that single layer coats.
Above-mentioned gained is once coated into ZIF-8@PDVB-VI 60mg, 40mL is added together with 0.5866g zinc nitrate hexahydrates
In methanol, 30min is vibrated after ultrasonic disperse 5min in room-temperature water bath, frequency of oscillation 150rpm makes Zn ions and PDVB-VI
The imidazole group on surface is saturated up to coordination.Another 40mL methanol dissolved with 1.2980g 2-methylimidazoles is quickly poured into
It states in solution, after persistent oscillation 60min, frequency of oscillation 150rpm.Products therefrom is centrifuged into 5min with rate 2000rpm, is discarded
Supernatant centrifuges again after adding methanol to be resuspended, and repeats aforesaid operations 3 times.Finally, secondary cladding ZIF-8@PDVB-VI are obtained, are such as schemed
Shown in 5.From Fig. 5 a and 5b as can be seen that on the basis of single layer coats, ZIF-8 nano particles can also continue to carry out multilayer
Cladding increases covering amount.
Embodiment 3
0.6mL divinylbenzenes and 0.0545gAIBN are dissolved into round-bottomed flask in 30mL acetonitriles and once sunk
Shallow lake pre-polymer solution.Primary sedimentation pre-polymer solution ultrasound 10min, logical nitrogen 15min are sealed after removing oxygen molecule, then will
The round-bottomed flask being sealed is put into constant temperature oscillation water-bath, is at the uniform velocity warming up to 60 DEG C from room temperature in 1.5h, frequency is shaken in water-bath
0-2h keeps 0rpm, and 140rpm is risen to after 2h, and precipitation polymerization reacts for 24 hours.The white product of generation uses acetonitrile and acetone successively
Washing removes residual monomer and interfering substance, is placed in vacuum drying chamber dry for 24 hours to get to the poly- diethyl of monodisperse in 60 DEG C
Alkene benzene microballoon (PDVB).
The poly- divinylbenzene microspheres 200mg of gained monodisperse and 38.1 μ L 1- vinyl imidazoles function monomers and 22mg are drawn
Hair agent AIBN is evenly spread to together obtains secondary precipitation pre-polymer solution in 30mL acetonitriles, by secondary precipitation pre-polymer solution ultrasound
Deaerate 10min, is sealed after logical nitrogen 15min, the secondary precipitation pre-polymer solution of sealing is put into 60 DEG C of water-bath constant temperature oscillators
For 24 hours, water-bath frequency of oscillation is maintained at 140rpm for middle reaction.The faint yellow product generated uses acetonitrile and acetone to wash successively, goes
Except residual monomer and interfering substance, it is placed in vacuum drying chamber dry for 24 hours to get to functional poly divinylbenzene microspheres in 60 DEG C
(PDVB-VI)。
It will be added in 40mL methanol, surpass together with gained functional poly divinylbenzene microspheres 50mg and 2.0g zinc nitrate hexahydrates
30min is vibrated in room-temperature water bath after sound dispersion 5min, frequency of oscillation 150rpm makes the miaow of Zn ions and the surfaces PDVB-VI
Oxazolyl group is saturated up to coordination.Another 40mL methanol dissolved with 5.533g2- methylimidazoles is quickly poured into above-mentioned solution,
After persistent oscillation 60min, frequency of oscillation 150rpm.Products therefrom is centrifuged into 5min with rate 1000rpm, discards supernatant, adds first
Alcohol centrifuges again after being resuspended, and repeats aforesaid operations 3 times.Finally, it obtains once coating ZIF-8@PDVB-VI.Nanometer ZIF-8 exists
The surfaces PDVB-VI form homogeneous close single layer cladding, and cladding thickness is about 100nm.
Claims (6)
1. a kind of preparation method of monodisperse nucleocapsid ZIF-8@PDVB-VI complex microspheres, it is characterised in that：Including following step
Suddenly：
(1) by divinylbenzene, initiator and reaction medium mixing, primary sedimentation pre-polymer solution is obtained, formula is as follows：Diethyl
Alkenyl benzene volume is 1-5%v, and v is reaction medium volume herein, and initiator quality 0.5-25%w, w is divinyl herein
The quality of benzene；Primary sedimentation pre-polymer solution ultrasound is deaerated, is sealed after logical nitrogen deoxygenation, under constant temperature water bath oscillating condition into
Row primary sedimentation polymerisation is dried after products therefrom washing to get to the poly- divinylbenzene microspheres of monodisperse；
(2) poly- divinylbenzene microspheres obtained by step (1) and 1- vinyl imidazoles and initiator reaction is evenly spread to together to be situated between
In matter, secondary precipitation pre-polymer solution is obtained, formula is as follows：Poly- divinylbenzene microspheres quality is 0.02-10%w1, w herein1For
Reaction medium quality, 1- vinyl imidazole quality are 0.01-1%v1, v1For reaction medium volume, initiator quality 0.5-
25%w2, w herein2For the quality of 1- vinyl imidazoles；Secondary precipitation pre-polymer solution ultrasound is deaerated, it is close after logical nitrogen deoxygenation
Envelope carries out secondary precipitation polymerisation under constant temperature water bath oscillating condition；It is dried to get to 1- ethylene after products therefrom washing
Base imidazoles functional poly divinylbenzene microspheres；
(3) by obtained by step (2) 1- vinyl imidazole functional poly divinylbenzene microspheres and zinc nitrate hexahydrate it is evenly dispersed
In reaction medium, room-temperature water bath oscillation reaches balance, obtains uniform mixture, oscillation is kept, by 2-methylimidazole
It is dispersed in reaction medium and pours into said mixture, continue oscillating reactions, detach solid product after reaction and obtain
To primary cladding ZIF-8@PDVB-VI nucleocapsid microballoons；The reaction medium dosage used twice in above-mentioned steps is equal, work(
The poly- divinylbenzene microspheres of energyization：Zinc nitrate hexahydrate：2-methylimidazole：The mass ratio of reaction medium total amount is 0.01-1 twice：
0.5：1-10：10-100.
2. preparation method according to claim 1, it is characterised in that：The primary cladding ZIF-8@PDVB- obtained by step (3)
The operation that the poly- divinylbenzene microspheres of VI nucleocapsid microballoon replacement functionizations repeat step (3) is primary secondary or multiple difference can
It is secondary three times or repeatedly cladding ZIF-8@PDVB-VI nucleocapsid microballoons.
3. preparation method according to claim 1 or 2, it is characterised in that：
The initiator is azodiisobutyronitrile；Reaction medium described in step (1) or step (2) be acetonitrile or acetonitrile with
The mixture of toluene；Reaction medium described in step (3) is methanol or one kind in water or two kinds；The ultrasound degassing operation
Time is 5-15min, and the time for leading to nitrogen deoxygenation operation is 5-15min.
4. preparation method according to claim 1 or 2, it is characterised in that：
The primary sedimentation polymerisation and secondary precipitation polymerisation carry out in water-bath constant temperature oscillator, and reaction temperature is equal
It it is 50-70 DEG C, the reaction time is 12-24h；The concussion frequency of primary sedimentation polymerisation is kept in 0-2h in step (1)
0-80rpm, later frequency of oscillation be maintained at 120-160rpm until primary sedimentation polymerisation terminate；It is secondary heavy in step (2)
Frequency is shaken in the polymerization process of shallow lake remains at 120-160rpm；Step (3) reaction in water-bath constant temperature oscillator into
It goes, concussion frequency is 120-160rpm, reaction time 0.2-2h in reaction process.
5. preparation method according to claim 1 or 2, it is characterised in that：
Washing operation described in step (1) or step (2) is that acetonitrile and acetone is used to wash successively, 50-70 DEG C of vacuum after washing
Dry 12-24h.
6. preparation method according to claim 1, it is characterised in that：
Described in step (3) detach solid product the specific steps are：Product centrifuges 5-15min with rate 1000-3000rpm,
It discards supernatant, is centrifuged again after adding methanol to be resuspended, repeat aforesaid operations 3-5 times.
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| CN111203273B (en) * | 2020-01-13 | 2022-11-29 | 辽宁大学 | Super-hydrophobic metal organic framework composite material based on porous polymer PDVB-vim and preparation method and application thereof |
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