CN107175053A - A kind of preparation method of the covalent organic framework complex microsphere of core shell structure - Google Patents
A kind of preparation method of the covalent organic framework complex microsphere of core shell structure Download PDFInfo
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- CN107175053A CN107175053A CN201710388941.0A CN201710388941A CN107175053A CN 107175053 A CN107175053 A CN 107175053A CN 201710388941 A CN201710388941 A CN 201710388941A CN 107175053 A CN107175053 A CN 107175053A
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- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/265—Adsorption chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/34—Size selective separation, e.g. size exclusion chromatography, gel filtration, permeation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- 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
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
Abstract
The present invention relates to a kind of preparation method of the covalent organic framework complex microsphere of core shell structure, this method is that silicon dioxide microsphere, first are constructed into primitive, second primitive is constructed and is dissolved in organic solvent, add after catalyst, at a certain temperature a kind of complex microsphere of core shell structure of Fast back-projection algorithm.Preparation process reaction condition of the present invention is gentle, method simple and yield is higher；Obtained covalent organic framework complex microsphere has good nucleocapsid pattern, the advantages of high-specific surface area, orderly aperture structure, good mechanical stability, heat endurance and chemical stability, it regard the microballoon as chromatographic stationary phases, chromatogram resistance to mass tranfer can be effectively reduced, improve height equivalent to a theoretical plate, finally realize the raising of post effect and separating degree；Using the microballoon as solid phase extraction filler, enrichment effect can be significantly improved.There is preferable application prospect in terms of organic molecule separation and concentration.
Description
Technical field
Preparation method field, more particularly to a kind of covalent organic framework of core shell structure are connected the present invention relates to covalent bond
The preparation method of complex microsphere.
Background technology
As life science, environmental science, Food Science and medical science etc. study continuing to bring out and developing for frontier,
High-resolution, high selectivity, pinpoint accuracy, high sensitivity and high-throughout separation analysis to realizing complex system propose higher
Requirement.Chromatographic technique promotes the development of above-mentioned related discipline all the time as a kind of powerful separation analysis means.Chromatogram is consolidated
The fixed core as chromatographic technique, is the foreword and focus in chromatogram research field all the time.Traditional bonded phase color
Spectrum uses silica gel for carrier, and different organic groups is bonded on Silica Surface by alkylation or silanization etc., so that
Substantially increase the selectivity of separation.Nevertheless, there is workable pH narrow ranges, mass transfer rate in such chromatographic stationary phases
It is low, the shortcomings of post pressure is high.High-specific surface area, resistance to mass tranfer are small, back-pressure is low, durable because it has for the chromatographic stationary phases of core shell structure
Property the features such as good, separating rate is fast and post effect is high by vast chromatogram research person extensive concern, as solving complicated sample in recent years
One of study hotspot that product are separated efficiently and rapidly.
Covalent organic framework material (Covalent Organic Frameworks, COFs) is that a class is connected by covalent bond
Porous crystalline material, with predictable structure, orderly arrangement mode, higher surface area, adjustable aperture, extremely low
Density, good heat and chemical stability the advantages of, in gas storage, photoelectric device, insoluble drug release, catalysis and divide in recent years
From etc. field receive significant attention.For separation field, COFs has regular pore passage structure, high-specific surface area, is easy to repair
The advantages of decorations, high chemically and thermally stability, make its as chromatographic stationary phases and SPE material the pole in terms of analysis is separated
It is with potential applications（Qian H L, Yang C X, Yan X P. Nature Communications. 2016, 7,
12104.; Yang C X, Liu C, Cao Y M, et al. Chemical Communications, 2015, 51,
12254-12257.; Lin G, Gao C, Zheng Q, et al. Chemical Communications, 2017,53,
3649-3652.）.However, develop novel synthetic method two dimension or three-dimensional COFs coatings is immobilized to micron or nanometer
The technological challenge of sternness is still faced with the carrier of yardstick.
The present invention is immobilized in micro-meter scale by COFs coatings by simple and quick synthetic method using silica as carrier
Silicon ball surface, and then the hybridization compounding microballoon with core shell structure is made.The core shell structure complex microsphere have high-specific surface area,
Duct shell structurre is homogeneous, pore-size distribution is narrow, high mechanical properties and many advantages, such as good chemically and thermally stability.Utilize silicon
π-πconjugation and intermolecular force between the COFs coatings of ball surface and medium or low pole organic molecule, will can be somebody's turn to do
Core shell structure complex microsphere is as chromatographic stationary phases or SPE material for medium or low pole organic molecule chromatogram point
From or enrichment.The core shell structure complex microsphere can significantly improve the specific surface area of stationary phase, effectively reduce the resistance of chromatogram mass transfer
Power and back-pressure, and then reduce the height equivalent to a theoretical plate of chromatogram, the raising of final realization theory post effect or bioaccumulation efficiency.So far, make
There is not been reported for the method for the standby covalent organic framework complex microsphere with core shell structure.
The content of the invention
In view of this, it is an object of the invention to provide a kind of preparation side of the covalent organic framework complex microsphere of core shell structure
Method, obtained complex microsphere has that high-specific surface area, duct shell structurre are homogeneous, pore-size distribution is narrow, high mechanical properties and good
Chemically and thermally stability many advantages, such as, as chromatographic stationary phases or SPE materials application in organic molecule point
There is preferable application prospect from enrichment.
The present invention is realized using following scheme：A kind of preparation method of the covalent organic framework complex microsphere of core shell structure,
It is characterized in that：Comprise the following steps：
Step S1：Silicon dioxide microsphere, first are constructed into primitive and second to construct primitive and be placed in organic solvent and uniformly mix；
Step S2：The mixture of gained ultrasound and is stirred at a certain temperature in the step S1, it is dispersed and then slow plus
Enter catalyst, the covalent organic framework complex microsphere of the reaction generation core shell structure；
Step S3：Complex microsphere made from the step S2 is placed in after centrifuge washing for several times respectively with tetrahydrofuran and ethanol
It is dried in vacuo in 150 DEG C.
Further, in the step S1, described first constructs primitive for terephthalaldehyde, equal benzene trioxin, 1,
3,5- trifonnyls phloroglucin, diphenyl-dimethanal, 1,3,5- tri-（4- formylphenyls）Benzene 1,3,6,8- tetra-（4- formylphenyls）
One kind in pyrene.
Further, in the step S1, described second constructs primitive for p-phenylenediamine, benzidine, 3,3 '-dihydroxy
Base benzidine, 1,3,5- triamine phenyl benzene, 1,3,5- tri-（4- formylphenyls）Amine, tetramine phenylethylene, 5,10,15,20- tetra-
One kind in (4- aminobenzenes) -21H, 23H- porphyrins.
Further, in the step S1, described organic solvent is one kind in dimethyl sulfoxide or metacresol.
Further, in the step S2, described catalyst is one kind in acetic acid or metal salts of trifluoromethane sulphonic acid.
Further, in the step S1, described silicon dioxide microsphere, first construct primitive 1 and second and construct base
The ratio between amount of material of member is 1：1.5：1~3；Preferred value is 1：1.5：2.
Further, in the step S1, described silicon dioxide microsphere quality and organic solvent mass ratio is 5：
2。
Further, in the step S2, the mass fraction that described catalyst quality accounts for gross mass is 1：30.
Further, in the step S2, reaction temperature is 20 ~ 120 DEG C, preferably 25 DEG C；Reaction time be 0.25 ~
72 h, preferably 0.5 h.
Further, the covalent organic framework complex microsphere of the obtained core shell structure is to as chromatographic stationary phases,
Or to be used to separating or being enriched with middle polarity or low pole organic molecule as solid phase extraction filler.
Compared to prior art, the invention has the advantages that：
1st, the covalent organic framework complex microsphere preparation condition for the core shell structure that the present invention is provided is gentle, raw material is cheap and easy to get and produces
Rate is higher；Obtained covalent organic framework complex microsphere has good nucleocapsid pattern, high-specific surface area, orderly aperture knot
The advantages of structure, good mechanical stability, heat endurance and chemical stability.
2nd, the covalent organic framework complex microsphere for the core shell structure that the present invention is provided can be carried effectively as chromatographic stationary phases
High component mass transfer velocity, reduces height equivalent to a theoretical plate, improves post effect and separating degree, shortens analysis time；Filled out as SPE
Material, because it has high reference area and action site, can significantly improve bioaccumulation efficiency, be separated in organic molecule with being enriched with
Aspect has preferable application prospect.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the covalent organic framework complex microsphere of silicon dioxide microsphere and the core shell structure of invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the covalent organic framework complex microsphere of silicon dioxide microsphere and the core shell structure of invention.
Fig. 3 is by silicon dioxide microsphere and the infrared spectrum of the covalent organic framework complex microsphere for the core shell structure invented
Figure.
Fig. 4 covalently has the nitrogen adsorption-desorption curve and graph of pore diameter distribution of skeleton complex microsphere for the core shell structure of invention.
Fig. 5 is to regard the covalent organic framework complex microsphere of the gained core shell structure of embodiment 1 as Stationary Phase for HPLC system
Chromatographic column post pressure and the flow velocity linear relationship chart obtained.
Fig. 6 is used for the separation color of 4 kinds of benzene homologues for the covalent organic framework complex microsphere chromatographic column obtained in embodiment 5
Spectrogram.
Fig. 7 is double to 5 kinds as SPE material for the covalent organic framework complex microsphere of the gained core shell structure of embodiment 1
The enrichment performance map of aldehydes matter.
Embodiment
Below in conjunction with the accompanying drawings and embodiment the present invention will be further described, but the present invention is not limited to following examples.
The raw material that the present invention is used can be bought in market, or can be synthesized with methods known in the art.
Embodiment 1：
The preparation of the covalent organic framework complex microsphere of core shell structure, it comprises the following steps：
80 mg silicon dioxide microspheres, the equal benzene trioxins of 48 mg, 82.9 mg benzidine are dispersed in 60 mL diformazans sub-
In sulfoxide solvent, the min of ultrasonic mixing 25 simultaneously adds 2 mL acetic acid, then keep ultrasonic 30 min, obtains being total to for the core shell structure
Valency organic backbone is combined silicon ball.Distinguish centrifuge washing for several times with tetrahydrofuran and ethanol, resulting materials are placed in 150 DEG C and dried.
A is the transmission electron microscope picture of silicon dioxide microsphere in embodiment 1 in Fig. 1, and surface shape is can be clearly seen that from figure
The smooth silica bare ball average grain diameter of looks is about 2 μm.B is the covalent organic of core shell structure made from embodiment 1 in Fig. 1
The transmission electron microscope picture of skeleton complex microsphere, it can be seen that it has obvious core shell structure, illustrates silicon dioxide microsphere successfully
Covalent organic framework shell structure in cladding.
A is the scanning electron microscope (SEM) photograph of silicon dioxide microsphere in embodiment 1 in Fig. 2, and surface shape is can be clearly seen that from figure
The smooth silica bare ball particle diameter of looks is at 2 μm or so.As shown in B in Fig. 1, it can be seen that become thick after surface modification
It is rough, illustrate that COFs coatings are substantially coated on silica silicon ball surface.
Fig. 3 is silicon dioxide microsphere (A in embodiment 1）With the covalent organic framework complex microsphere for the core shell structure invented
(B) infrared spectrogram.From infrared spectrum it can be seen that：（A）In figure, silicon ball has bright at 3550 cm-1 and 2370 cm-1
Aobvious absworption peak, illustrates the characteristic absorption peak of silicone hydroxyl present in silicon ball and the unsaturated carbonnitrogen bond of silicon ball surface modification.
There is strong absworption peak at 802 cm-1 and 1101cm-1, indicate Si-O-Si feature stretching vibration；（B）In figure, nucleocapsid knot
The covalent organic framework complex microsphere of structure represents two in 3030 cm-1 and 2880 cm-1 absworption peak and constructs primitive phenyl ring
There is very strong absworption peak in upper unsaturated hydrocarbon characteristic absorption peak, 1620 cm-1 positions, illustrate that constructing both primitives occurs seat
The reaction of husband's alkali has successfully formed imine linkage（-C=N-）.In addition, it can also be seen that very strong Si- at 802 cm-1 and 1101 cm-1
O-Si absworption peaks.Pass through contrast（A）With（B）Figure, it can be seen that covalent organic framework material successfully coating in silicon dioxide meter
Face.
Fig. 4 is nitrogen adsorption-desorption curve under 77K of the covalent organic framework complex microsphere of the core shell structure of invention
And pore size distribution curve（It is embedded）.Adsorption-desorption curve can be classified as the IV type thermoisopleths of IUPAC classification, show that material has Jie
Pore structure；Shown from pore size distribution curve, the microballoon has narrower pore-size distribution, concentrates on 2.7 nm or so.Pass through absorption
The maximum point of relative pressure on curve（P/P0）Corresponding adsorbance calculates sample total pore volume for 0.554 cm3/g, BET knots
Fruit shows that its specific surface area reaches 172.3 m2/g.
Embodiment 2：
Using the covalent organic framework complex microsphere of core shell structure made from embodiment 1 as chromatographic stationary phases, using dry-packing
Method be packed into internal diameter for 2.1 mm, length is 50 mm empty stainless steel short column, is needed before filling successively with acetone, secondary
Water and methanol are cleaned by ultrasonic for several times.One end of void column connects vacuum source during dress post, and the other end loads onto funnel, dry nucleocapsid knot
The covalent organic framework complex microsphere of structure is slowly fed wherein, is gently tapped post jamb, microballoon is fallen into post.Can during filling microballoon
Ethanol, which is added dropwise, makes it closer.With the mobile phase that flow velocity is 0.1 mL/min on high performance liquid chromatograph after the completion of filling（Water：
Acetonitrile=10:90, v:v）Balance is rinsed for a long time, that is, obtains that filler is close and uniform chromatographic column.Finally in Liquid Chromatography mode
Under, the post pressure in lower covalent organic framework complex microsphere chromatographic column different in flow rate is investigated respectively.As shown in Figure 5, post pressure and flowing
Phase flow velocity is linear related (R2=0.9988).This not only shows that the material meets the primary condition as Stationary Phase for HPLC,
And reflect that uniform filling is close in pillar to a certain extent.
Embodiment 3：
In liquid chromatogram（HPLC）Under pattern, with acetonitrile：The aqueous solution（5：95, v/v）For mobile phase A, water：Acetonitrile solution（5：95,
v/v）For Mobile phase B, chromatographic condition is 55%B；Flow rate pump is 0.2 mL/min, and Detection wavelength is 214 nm；Thiocarbamide（20
ppm）, benzene（100 ppm）, toluene（100 ppm）, ethylbenzene（100 ppm）, naphthalene（100 ppm）Mixed liquor embodiment 2 be made
Chromatographic column on realize the separation of efficient selective, its chromatographic fractionation figure is as shown in fig. 6, the peak in chromatogram is followed successively by 1：Sulphur
Urea, 2：Benzene, 3：Toluene, 4：Ethylbenzene, 5：Naphthalene.
Embodiment 4：
The covalent organic framework complex microsphere for the core shell structure that embodiment 1 is synthesized is used as a kind of SPE material.In liquid phase
Chromatogram（HPLC）Under pattern, with acetonitrile/water solution（55：45, v/v）For mobile phase, flow rate pump is 1mL/min, and Detection wavelength is
275 nm, 5 kinds of bisphenols（Bisphenol S：4,4 dihydroxydiphenyl methane, Bisphenol F：4,4 dihydroxydiphenyl methane, bis-phenol
A：2,2- bis-（4- hydroxy phenyls）Propane, bisphenol b：2,2- bis- (4- hydroxy phenyls) butane, bisphenol AF：(the 4- hydroxy benzenes of 2,2'- bis-
Base)-HFC-236fa）Each 100 ppm standard mixed liquor is separated.The complex microsphere synthesized by embodiment 1 is extracted to it
Afterwards, supernatant is taken with same chromatographic condition sample introduction.Compared with aggregate sample, almost do not occur chromatographic peak in supernatant, show
Bisphenol is most of to be enriched on complex microsphere.After being eluted 3 times to the microballoon for being enriched bisphenol with methanol,
By eluent direct injected.As seen from Figure 7, the peak area of eluent sample introduction is far above direct injected, shows that this is compound micro-
The concentration effect of ball is obvious, it is adaptable to be used as SPE material.Chromatographic fractionation figure as shown in fig. 7, the peak in chromatogram successively
For 1：Bisphenol S；2：Bisphenol F；3：Bisphenol-A；4：Bisphenol b；5：Bisphenol AF.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (10)
1. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure, it is characterised in that：Comprise the following steps：
Step S1：Silicon dioxide microsphere, first are constructed into primitive and second to construct primitive and be placed in organic solvent and uniformly mix；
Step S2：The mixture of gained ultrasound and is stirred at a certain temperature in the step S1, it is dispersed and then slow plus
Enter catalyst, the covalent organic framework complex microsphere of the reaction generation core shell structure；
Step S3：Complex microsphere made from the step S2 is placed in after centrifuge washing for several times respectively with tetrahydrofuran and ethanol
It is dried in vacuo in 150 DEG C.
2. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure according to claim 1, its feature exists
In：In the step S1, described first to construct primitive be between terephthalaldehyde, equal benzene trioxin, 1,3,5- trifonnyls
Benzenetriol, diphenyl-dimethanal, 1,3,5- tri-（4- formylphenyls）Benzene 1,3,6,8- tetra-（4- formylphenyls）One kind in pyrene.
3. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure according to claim 1, its feature exists
In：In the step S1, described second constructs primitive for p-phenylenediamine, benzidine, 3,3 '-dihydroxybiphenyl amine, 1, and 3,
5- triamine phenyl benzene, 1,3,5- tri-（4- formylphenyls）Amine, tetramine phenylethylene, 5,10,15,20- tetra- (4- aminobenzenes) -21H,
One kind in 23H- porphyrins.
4. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure according to claim 1, its feature exists
In：In the step S1, described organic solvent is one kind in dimethyl sulfoxide or metacresol.
5. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure according to claim 1, its feature exists
In：In the step S2, described catalyst is one kind in acetic acid or metal salts of trifluoromethane sulphonic acid.
6. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure according to claim 1, its feature exists
In：In the step S1, described silicon dioxide microsphere, first construct primitive 1 and second construct primitive material amount it
Than for 1：1.5：1~3；Preferred value is 1：1.5：2.
7. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure according to claim 1, its feature exists
In：In the step S1, described silicon dioxide microsphere quality and organic solvent mass ratio is 5：2.
8. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure according to claim 1, its feature exists
In：In the step S2, the mass fraction that described catalyst quality accounts for gross mass is 1：30.
9. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure according to claim 1, its feature exists
In：In the step S2, reaction temperature is 20 ~ 120 DEG C, preferably 25 DEG C；Reaction time is 0.25 ~ 72 h, preferably 0.5
h。
10. a kind of preparation method of the covalent organic framework complex microsphere of core shell structure according to claim 1, its feature exists
In：The covalent organic framework complex microsphere of the obtained core shell structure is to as chromatographic stationary phases, or to be used as solid phase
Extraction stuffing is used to separating or being enriched with middle polarity or low pole organic molecule.
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