CN101845125B - Method for preparing molecular imprinted polymer on surface of carbon microspheres - Google Patents
Method for preparing molecular imprinted polymer on surface of carbon microspheres Download PDFInfo
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- CN101845125B CN101845125B CN2010101378226A CN201010137822A CN101845125B CN 101845125 B CN101845125 B CN 101845125B CN 2010101378226 A CN2010101378226 A CN 2010101378226A CN 201010137822 A CN201010137822 A CN 201010137822A CN 101845125 B CN101845125 B CN 101845125B
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Abstract
The invention relates to a method for preparing a molecular imprinted polymer on the surface of carbon microspheres, which comprises the following steps of: preparing the carbon microspheres by using acetylene gas; and preparing imprinted carbon microspheres on a three-neck flask, a water bath and an electrothermal stirring vessel, namely performing oxidation treatment on the carbon microspheres and then performing surface modification on the oxidized carbon microspheres to prepare the imprinted carbon microspheres and form irregular hole prints on the surface of the carbon microspheres. The preparation method has the advantages of advanced and reasonable process, short process flow, less environmental pollution, attractive appearance of a product, high purity of 99 percent and high product yield of 91 percent; the imprinted carbon microspheres are black and round particles with the particle diameter of 100 to 200nm and can be matched with various chemical substances; the method is an ideal method for preparing the imprinted carbon microspheres; and the product can be applied to the fields of pharmacy and various industries.
Description
Technical field
The present invention relates to a kind of preparation method of molecular imprinted polymer on surface of carbon microspheres, belong to the technical field of surface-functionalized modification of organic carbon material-carbosphere and application.
Background technology
Molecular imprinting; It is a new branch of science; Be that template molecule is branded on certain matrix; Make matrix have special selectivity and binding ability, thereby can be used for separation, enrichment and the detection etc. of template molecule, show good prospects for application in fields such as chiral separation, SPE, enrichment, detection, enzyme simulation, chemobionics transmitters template molecule.
The matrix of molecular engram material can be inorganic materials; For example silica gel, aluminum oxide etc. also can be polymer materials, but the recognition site of polymer microballoon is mostly inner at polymer microballoon; When discerning than macromole, the existence of diffusional resistance can cause molecule to be identified to combine difficulty with recognition site.
Carbosphere; Be CMSs; It is a kind of material that well is used as surface molecule print matrix; Have abundant bonding position, stable potential of hydrogen, good thermostability and mechanical property after the CMSs finishing, and at its surface grafting polymethyl acrylic acid, for the carbosphere value added applications is laid a good foundation.
In petroleum products, mostly contain objectionable impuritiess such as sulphur, phosphorus, mostly the form with sulfide exists; In low-sulfur 50ppm and super low sulfur 10ppm oil product; It is very difficult how sloughing sulphur, if use absorption method, adopts molecular imprinted polymer on surface of carbon microspheres to carry out desulfurization; It is a good doctor treatment; Neither reduce the octane value of oil product, separate sulfur ethers and thiophene sulfocompounds well again are so be a kind of good sulfur method with the sulfocompound in the molecular imprinted polymer on surface of carbon microspheres absorption oil product.
The preparation of molecular imprinted polymer on surface of carbon microspheres is a new technology, and application parameter, detection characterize all to be needed further to inquire into and research.
Summary of the invention
Goal of the invention
The object of the invention is exactly the practical situation to background technology; Adopt brand-new technology of preparing, the preparation carbosphere carries out oxide treatment then earlier; And carry out modification; Process molecular imprinted polymer on surface of carbon microspheres, make preparation trace carbosphere become possibility, to be applied in pharmacy and multiple industrial circle.
Technical scheme
The chemical substance material that the present invention uses is: dibenzothiophene, TGM 1, α-Jia Jibingxisuan, Diisopropyl azodicarboxylate, chloroform, absolute ethyl alcohol, methyl alcohol, glacial acetic acid, γ-(methacryloxypropyl) propyl trimethoxy silicane, deionized water, potassium permanganate, sulfuric acid, oxalic acid, acetylene, nitrogen, argon gas, its combination consumption is following: with gram, milliliter, centimetre
3Be measure unit
Dibenzothiophene: C
12H
8S, 0.369g ± 0.001g
TGM 1: EDMA, C
10H
14O
4, 4ml ± 0.01ml
α-Jia Jibingxisuan: MAA, C
4H
6O
2, 1ml ± 0.01ml
Diisopropyl azodicarboxylate: AIBN, C
8H
12N
4, 0.065g ± 0.001g
Chloroform: CHCl
3, 20ml ± 0.01ml
Absolute ethyl alcohol: C
2H
5OH, 10000ml ± 10ml
Methyl alcohol: CH
3OH, 2000ml ± 10ml
Glacial acetic acid: C
2H
4O
2, 2000ml ± 10ml
γ-(methacryloxypropyl) propyl trimethoxy silicane: KH-570, C
10H
20O
5Si, 10ml ± 0.01ml
Potassium permanganate: KMnO
4, 0.5g ± 0.01g
Sulfuric acid: H
2SO
4, 100ml ± 1ml
Oxalic acid: H
2C
2O
4, 1000ml ± 1ml
Deionized water: H
2O, 20000ml ± 100ml
Acetylene: C
2H
4, 20000cm
3± 100cm
3
Argon gas: Ar, 200000cm
3± 100cm
3
Nitrogen: N
2, 200000cm
3± 100cm
3
The preparation method is following:
(1) selected chemical substance material
The chemical substance material that preparation is used will carry out selected, and carries out quality purity control:
Dibenzothiophene: solid-state solid 98%
TGM 1: liquid liquid 98%
α-Jia Jibingxisuan: liquid liquid 99%
Diisopropyl azodicarboxylate: solid-state solid 99%
Chloroform: liquid liquid 99%
Absolute ethyl alcohol: liquid liquid 99.7%
Methyl alcohol: liquid liquid 99.5%
Glacial acetic acid: liquid liquid 99.5%
γ-(methacryloxypropyl) propyl trimethoxy silicane: liquid liquid 99.5%
Deionized water: liquid liquid 99.99%
Potassium permanganate: solid-state solid 99.5%
Sulfuric acid: liquid strength of fluid 36%
Oxalic acid: liquid liquid 99.5%
Acetylene: gaseous state gas 99.0%
Argon gas: gaseous state gas 99.0%
Nitrogen: gaseous state gas 99.0%
(2) preparation carbosphere
1. preparation is to carry out in tube type high-temperature furnace with acetylene+argon gas;
2. with deionized water 1000ml lavation cleaning cleaning tube type high-temperature furnace silica tube, make its cleaning, dry then;
3. stop up the silica tube two ends, make its sealing;
4. connect tunger tube, open argon gas valve, argon bottle, feed argon gas, argon gas input speed 200cm
3/ min drives away obnoxious flavour in the silica tube, time 20min;
5. open the High Temperature Furnaces Heating Apparatus well heater, make the interior temperature of stove rise to 950 ℃ ± 5 ℃, 23 ℃/min of heat-up rate by 20 ℃;
6. connect acetylene hose, open acetylene valve, acetylene cylinder, feed acetylene gas, acetylene input speed 80cm
3/ min, acetylene gas gets into silica tube under carrier gas-argon gas drives, and acetylene gas carries out modality under heated condition, process carbosphere, time 120min ± 2min;
Acetylene gas under 950 ℃ ± 5 ℃ states, carries out modality, vapour deposition on the tube wall of silica tube high temperature section under argon shield, converted into solid-stately by gaseous state, generates carbosphere;
In the modality process, will carry out chemical reaction, reaction formula is following:
In the formula:
C: carbosphere
H
2: hydrogen
7. close the acetylene valve, stop to import acetylene gas; Close the High Temperature Furnaces Heating Apparatus well heater, stop heating;
8. the carbosphere product in the silica tube cools to 20 ℃ ± 2 ℃ with the furnace under argon shield;
9. close the argon gas valve, stop defeated argon gas;
10. take out silica tube, collect the carbosphere product on the quartzy tube wall;
(3) grind, sieve, purifying, thinning processing carbosphere
The carbosphere product is ground with agate mortar, sieve, grind, sieving repeats, retain the carbosphere fine powder with 650 eye mesh screens;
(4) oxide treatment carbosphere
1. the oxide treatment carbosphere stirs on the ware at there-necked flask, cleansing bath tub, electric heating and carries out, and under nitrogen protection, water cycle condensing state, accomplishes;
2. carbosphere 1g is added in the there-necked flask by addition funnel;
With potassium permanganate 0.5g+ deionized water 32mL, be mixed with 0.1mol/L solution, add in the there-necked flask by addition funnel;
Sulfuric acid 20ml is added in the there-necked flask by addition funnel;
3. open water inlet pipe, the rising pipe of water cycle prolong, carry out the water cycle condensation;
4. open nitrogen valve, nitrogengas cylinder, to there-necked flask input nitrogen, input speed 50cm
3/ min;
5. open electric heating and stir ware, temperature rises to 80 ℃ ± 2 ℃ by 20 ℃, and begins to stir, and carries out oxidizing reaction;
6. stir, oxidization time 360min ± 2min becomes: oxide soln;
7. in the carbosphere oxidising process, will carry out chemical reaction, reaction formula is following:
In the formula:
C-OH: hydroxyl carbosphere
MnO
2: Manganse Dioxide
K
2SO
4: vitriolate of tartar
8. after the oxidizing reaction, close electric heating and stir ware, make there-necked flask and interior oxide soln thereof be cooled to 20 ℃ ± 2 ℃ with cleansing bath tub;
9. suction filtration
Oxide soln is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper; Retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
10. the pH value is controlled in deionized water wash, suction filtration, measurement
The product filter cake is placed beaker, add deionized water 200ml, use the whisking appliance agitator treating;
Then washings is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
Deionized water wash, suction filtration repeat ten times;
In washing suction filtration process, measure the oxide soln potential of hydrogen, be neutral, the pH value is 7;
Washing gets the product filter cake behind the suction filtration;
Place vacuum drying oven to carry out drying treatment the product filter cake, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness 10Pa, time of drying, 480min got after the drying: the carbonoxide microballoon;
The carbonoxide microballoon is placed beaker, add oxalic acid 200ml, wash, stir 30min, on walls of beaker, have great amount of bubbles to emerge, become: washing soln;
Washing soln is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper, the product filter cake is retained on the filter paper, and waste liquid is evacuated in the filter flask;
Carbonoxide microballoon after the washing is placed beaker, add deionized water 300ml, agitator treating carries out suction filtration with three layers of middling speed qualitative filter paper then;
Washing, suction filtration repeat ten times;
In washing suction filtration process, measure solution acid alkalinity, be neutral, the pH value is 7;
Place vacuum drying oven to carry out vacuum-drying the carbonoxide microballoon of washing behind the suction filtration, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness is 10Pa, time of drying 480min;
After the drying: the carbonoxide microballoon;
(5) modification carbosphere
1. the modification carbosphere stirs on the ware at there-necked flask, cleansing bath tub, electric heating and carries out, and under nitrogen protection, water cycle condensing state, accomplishes;
2. the carbonoxide microballoon is added in the there-necked flask;
Absolute ethyl alcohol 100ml is added in the there-necked flask;
Deionized water 100ml is added in the there-necked flask;
Properties-correcting agent γ-(methacryloxypropyl) propyl trimethoxy silicane 10ml is placed there-necked flask;
3. open water inlet pipe, the rising pipe of water cycle prolong, carry out the water cycle condensation;
4. open nitrogen valve, nitrogengas cylinder, input nitrogen, nitrogen input speed 50cm
3/ min;
5. open electric heating and stir ware, temperature rises to 55 ℃ ± 2 ℃ by 20 ℃, and stirs;
6. heated and stirred 840min ± 2min carries out the modification reaction;
7. in the modification reaction, chemical reaction will take place, reaction formula is following:
In the formula:
C-OH: hydroxyl carbosphere
C-C
9H
17O
5Si: the carbosphere of silylanization
8. behind modification, the modified-reaction, close electric heating and stir ware, stop heated and stirred, make it under nitrogen, water cycle condensing state, be cooled to 20 ℃ ± 2 ℃; : modification solution;
9. suction filtration
Modification solution is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
10. vacuum-drying
Place vacuum drying oven to carry out drying the product filter cake, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness 10pa, time of drying 480min ± 2min;
After the drying: the modification carbosphere;
(6) preparation trace carbosphere
1. prepare the trace carbosphere and on there-necked flask, electric heating stirring ware, cleansing bath tub, carry out, under nitrogen protection, water cycle condensation, accomplish;
2. the modification carbosphere is added in the there-necked flask, dibenzothiophene 0.369g is added in the there-necked flask, chloroform 20ml is added in the there-necked flask, α-Jia Jibingxisuan 1ml is added in the there-necked flask;
3. open the water inlet pipe rising pipe of water cycle prolong, carry out the water cycle condensation;
Open nitrogen valve, nitrogengas cylinder, input nitrogen, nitrogen input speed 50cm
3/ min;
Open electric heating and stir ware, make temperature rise to 60 ℃ ± 2 ℃, and begin to stir by 20 ℃;
4. evenly stir 30min ± 2min, modification carbosphere and dibenzothiophene, α-Jia Jibingxisuan are fully acted on;
5. add initiator Diisopropyl azodicarboxylate 0.065g, add linking agent TGM 1 4ml, continue to stir 1440min, and react;
6. in preparation trace carbosphere process, chemical reaction will take place, reaction formula is following:
In the formula:
C-C
35H
45O
11SSi: the trace carbosphere that contains dibenzothiophene
7. after the reaction, close electric heating and stir ware, make there-necked flask in cleansing bath tub, under nitrogen protection, under the water cycle condensation, naturally cool to 20 ℃ ± 2 ℃, become: trace carbosphere reaction soln;
8. suction filtration
Trace carbosphere reaction soln is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
9. absolute ethanol washing, suction filtration
Product filter cake behind the suction filtration is placed beaker, add absolute ethyl alcohol 100ml, agitator treating carries out suction filtration with three layers of middling speed qualitative filter paper then;
Washing, suction filtration repeat ten times;
10. methyl alcohol+glacial acetic acid washing, suction filtration, remove dibenzothiophene
Compounding methanol+glacial acetic acid mixing solutions
With methyl alcohol 720ml, glacial acetic acid 80ml places beaker, stirs 10min, becomes: mixing solutions;
The trace carbosphere is placed the mixing solutions in the beaker, use the whisking appliance agitator treating;
On filter flask, carry out suction filtration then with three layers of middling speed qualitative filter paper;
Washing, suction filtration repeat ten times;
Remove dibenzothiophene after the washing, form the hole, after the washing: the trace carbosphere;
The trace carbosphere is placed beaker, add absolute ethyl alcohol 100ml, agitator treating;
On filter flask, carry out suction filtration then with three layers of middling speed qualitative filter paper;
Washing, suction filtration repeat ten times;
Remove methyl alcohol, glacial acetic acid after the washing, get final product: trace carbosphere filter cake;
Place vacuum drying oven dry washing, final product carbosphere filter cake behind the suction filtration, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness 10Pa, time of drying 480min ± 2min;
Get final product after the drying: the trace carbosphere; That is: black powder trace carbosphere;
(7) detect, chemically examine, analyze, characterize
Color and luster, pattern, structure, composition, chemical physics performance, absorbancy, the concentration of trace carbosphere to preparation detects, analyzes, characterizes;
Carry out morphology analysis with field emission scanning electron microscope;
Carry out thermal stability analysis with thermogravimetric analyzer;
Carry out the surface functional group analysis with IR;
Carry out absorbance measuring with ultraviolet spectrophotometer;
Conclusion: the trace carbosphere is the black powder granule, and particle diameter is 100-200nm, and the carbosphere surface is irregular hollow cavity shaped.
(8) product stores
Airtight being stored in the water white Glass Containers of trace carbosphere product to preparation places drying, clean environment, waterproof, sun-proof, moistureproof, acid-proof alkali salt erosion, 20 ℃ ± 2 ℃ of storing temps, relative humidity≤10%.
The preparation of described trace carbosphere, be the carbon raw material with the acetylene gas, be carrier gas and shielding gas with the argon gas, be oxygenant with potassium permanganate, sulfuric acid, be washing composition with absolute ethyl alcohol, methyl alcohol, oxalic acid, glacial acetic acid, deionized water; Be shielding gas with nitrogen, be properties-correcting agent with γ-(methacryloxypropyl) propyl trimethoxy silicane; Be linking agent with the TGM 1, be initiator, be solvent, be trace carbosphere hole template with the dibenzothiophene with the chloroform with the Diisopropyl azodicarboxylate.
Described trace carbosphere is black, circle, powder granule shape, and particle diameter is 100-200nm, and the trace on the particle is irregular hole distribution.
The preparation of described carbosphere is carried out in tube type high-temperature furnace, and its preparation state is: on High Temperature Furnaces Heating Apparatus 1 top is resistance heater 2; High Temperature Furnaces Heating Apparatus 1 inner bottom part is a track 4; And connect track unit 5, and on track 4, put silica tube 3, silica tube 3 stretches in the High Temperature Furnaces Heating Apparatus on track 4; Silica tube 3 left parts are provided with plug 17, plug 17 top UNICOM acetylene hoses 8, acetylene valve 7, acetylene cylinder 6, bottom UNICOM tunger tube 11, argon gas valve 10, argon bottle 9; Silica tube 3 right parts are provided with plug 18, parallelly connected pass-out tracheae 16, and left part is that low temperature section 12, right part are that low temperature section 14, middle part are high temperature section 13 in the silica tube 3, is carbosphere product 15 on high temperature section 13 tube walls.
The preparation of described trace carbosphere, its oxidation, modification, trace all carry out in there-necked flask, and its preparation state is: there-necked flask 23 places on the cleansing bath tub 22; Cleansing bath tub 22 places electric heating to stir on the ware 21; Electric heating stirs ware 21 and is provided with image display 24, PL 25, trip switch 26; Be water-bath water 36 in the cleansing bath tub 22; There-necked flask 23 tops are provided with nitrogen tube 29, addition funnel 30, water cycle prolong 31; Nitrogen tube 29 connects nitrogen valve 28, nitrogengas cylinder 27; Water cycle prolong 31 connects water inlet pipe 33, rising pipe 34; Top is production well 32; There-necked flask 23 inner bottom parts are carbosphere 37, mixing solutions 38, and top is nitrogen 35.
The moulding preparation of described trace carbosphere is accomplished under anhydrous state.
Beneficial effect
The present invention compares with background technology has tangible advance, has adopted brand-new preparation technology's flow process, prepares carbosphere with acetylene gas earlier, stirs preparation trace carbosphere product on the ware at there-necked flask, cleansing bath tub, electric heating then; Earlier carbosphere is carried out oxide treatment, carry out finishing then, process the trace carbosphere at last; This preparing method's technology is tight, rationally advanced, and the product pattern is good, for the circular powder granule shape of black, particle diameter are 100-200nm; The carbosphere trace is obvious, is irregular hole shape, can mate with the number of chemical material; Product purity is high, can reach 99%, and product yield is high; Can reach 89%, be the very good method for preparing the nano print carbosphere, and its product can be used at chemical industry, pharmacy and multiple industrial circle.
Description of drawings
Fig. 1 prepares state graph for carbosphere
Fig. 2 prepares state graph for the trace carbosphere
Fig. 3 amplifies 10000 times of shape appearance figures for carbosphere
Fig. 4 amplifies 50000 scanning shape appearance figures for the trace carbosphere
Fig. 5 is a trace carbosphere infrared spectrogram
Fig. 6 is trace carbosphere thermogravimetric analysis figure
Fig. 7 is trace carbosphere curve of adsorption kinetics figure
Shown in the figure, list of numerals is following:
1, High Temperature Furnaces Heating Apparatus, 2, resistance heater, 3, silica tube, 4, track, 5, the track unit, 6, acetylene cylinder; 7, acetylene valve, 8, acetylene hose, 9, argon bottle, 10, the argon gas valve, 11, tunger tube, 12, low temperature section; 13, high temperature section, 14, low temperature section, 15, the carbosphere product, 16, escape pipe, 17, plug, 18, plug; 21, electric heating stirs ware, and 22, cleansing bath tub, 23, there-necked flask, 24, image display, 25, PL, 26, trip switch; 27, nitrogengas cylinder, 28, nitrogen valve, 29, nitrogen tube, 30, addition funnel, 31, the cool pipe that coagulates of water cycle, 32, production well; 33, water-in, 34, water outlet, 35, nitrogen, 36, water-bath water, 37, carbosphere, 38, mixing solutions.
Embodiment
Below in conjunction with accompanying drawing the present invention is further specified:
Shown in Figure 1, for carbosphere prepares state graph, each location, connecting relation want correct.
Acetylene gas is that carbosphere prepares raw material, and argon gas is carrier gas and shielding gas, also can drive away objectionable impurities in the silica tube, and its gas flow is wanted strict control.
High temperature section in the silica tube is that the gas phase of carbosphere product generates section.
Shown in Figure 2, for the trace carbosphere prepares state graph, each location, connecting relation want correct.
Oxidation, modification, the trace moulding of trace carbosphere in the preparation process all accomplished in there-necked flask, all be under nitrogen protection, under the water cycle condensing state, electrically heated stirs down and accomplishes according to the order of sequence, each operation is wanted strict control value, operates according to the order of sequence.
The value of the chemical substance that preparation is used is to confirm by the scope that is provided with in advance, with gram, milliliter, centimetre
3Be measure unit, when technology is produced, with kilogram, liter, rice
3Be measure unit.
The there-necked flask that preparation is used, cleansing bath tub, electric heating stir ware, beaker, container etc. all will keep clean, in case generate by product.
Shown in Figure 3, be the carbosphere shape appearance figure, can know among the figure: the carbosphere uniform particles is irregular alignment, ruler units 200nm.
Shown in Figure 4, be trace carbosphere shape appearance figure, can know among the figure: carbosphere particle surface overlie polymer layer is irregular hollow cavity shaped, ruler units 100nm.
Shown in Figure 5, be trace carbon ball infrared spectrogram, ordinate zou is that transsmissivity, X-coordinate are wave number, can know among the figure: 1153cm
-1The place is C-O stretching vibration peak, 1627cm
-1The place is C=C stretching vibration peak, 1727cm
-1The place is C=O stretching vibration peak, the 3433cm of carboxyl
-1The place is the stretching vibration peak of O-H.
Shown in Figure 6, be trace carbosphere thermogravimetric analysis figure, can know among the figure: ordinate zou is that rate of weight loss, X-coordinate are temperature, begins to take place thermolysis at 260 ℃, and to 480 ℃ of end, surface aggregate thing rate of weight loss is 40%.
Shown in Figure 7, be trace carbosphere curve of adsorption kinetics figure, ordinate zou is that adsorptive capacity, X-coordinate are adsorption time, shows that the trace carbosphere reaches balance time to the absorption of dibenzothiophene and needs 5h.
Claims (6)
1. the preparation method of a molecular imprinted polymer on surface of carbon microspheres; It is characterized in that: the chemical substance material of use is: dibenzothiophene, TGM 1, α-Jia Jibingxisuan, Diisopropyl azodicarboxylate, chloroform, absolute ethyl alcohol, methyl alcohol, glacial acetic acid, γ-(methacryloxypropyl) propyl trimethoxy silicane, deionized water, potassium permanganate, sulfuric acid, oxalic acid, acetylene, nitrogen, argon gas, its combination consumption is following: with gram, milliliter, centimetre
3Be measure unit
Dibenzothiophene: C
12H
8S, 0.369g ± 0.001g
TGM 1: EDMA, C
10H
14O
4, 4ml ± 0.01ml
α-Jia Jibingxisuan: MAA, C
4H
6O
2, 1ml ± 0.01ml
Diisopropyl azodicarboxylate: AIBN, C
8H
12N
4, 0.065g ± 0.001g
Chloroform: CHCl
3, 20ml ± 0.01ml
Absolute ethyl alcohol: C
2H
5OH, 10000ml ± 10ml
Methyl alcohol: CH
3OH, 2000ml ± 10ml
Glacial acetic acid: C
2H
4O
2, 2000ml ± 10ml
γ-(methacryloxypropyl) propyl trimethoxy silicane: KH-570, C
10H
20O
5Si, 10ml ± 0.01ml
Potassium permanganate: KMnO
4, 0.5g ± 0.01g
Sulfuric acid: H
2SO
4, 100ml ± 1ml
Oxalic acid: H
2C
2O
4, 1000ml ± 1ml
Deionized water: H
2O, 20000ml ± 100ml
Acetylene: C
2H
4, 20000cm
3± 100cm
3
Argon gas: Ar, 200000cm
3± 100cm
3
Nitrogen: N
2, 200000cm
3± 100cm
3
The preparation method is following:
(1) selected chemical substance material
The chemical substance material that preparation is used will carry out selected, and carries out quality purity control:
Dibenzothiophene: solid-state solid 98%
TGM 1: liquid liquid 98%
α-Jia Jibingxisuan: liquid liquid 99%
Diisopropyl azodicarboxylate: solid-state solid 99%
Chloroform: liquid liquid 99%
Absolute ethyl alcohol: liquid liquid 99.7%
Methyl alcohol: liquid liquid 99.5%
Glacial acetic acid: liquid liquid 99.5%
γ-(methacryloxypropyl) propyl trimethoxy silicane: liquid liquid 99.5%
Deionized water: liquid liquid 99.99%
Potassium permanganate: solid-state solid 99.5%
Sulfuric acid: liquid strength of fluid 36%
Oxalic acid: liquid liquid 99.5%
Acetylene: gaseous state gas 99.0%
Argon gas: gaseous state gas 99.0%
Nitrogen: gaseous state gas 99.0%
(2) preparation carbosphere
1. preparation is to carry out in tube type high-temperature furnace with acetylene+argon gas;
2. with deionized water 1000ml lavation cleaning cleaning tube type high-temperature furnace silica tube, make its cleaning, dry then;
3. stop up the silica tube two ends, make its sealing;
4. connect tunger tube, open argon gas valve, argon bottle, feed argon gas, argon gas input speed 200cm
3/ min drives away obnoxious flavour in the silica tube, time 20min;
5. open the High Temperature Furnaces Heating Apparatus well heater, make the interior temperature of stove rise to 950 ℃ ± 5 ℃, 23 ℃/min of heat-up rate by 20 ℃;
6. connect acetylene hose, open acetylene valve, acetylene cylinder, feed acetylene gas, acetylene input speed 80cm
3/ min, acetylene gas gets into silica tube under carrier gas-argon gas drives, and acetylene gas carries out modality under heated condition, process carbosphere, time 120min ± 2min;
Acetylene gas under 950 ℃ ± 5 ℃ states, carries out modality, vapour deposition on the tube wall of silica tube high temperature section under argon shield, converted into solid-stately by gaseous state, generates carbosphere;
In the modality process, will carry out chemical reaction, reaction formula is following:
In the formula:
C: carbosphere
H
2: hydrogen
7. close the acetylene valve, stop to import acetylene gas; Close the High Temperature Furnaces Heating Apparatus well heater, stop heating;
8. the carbosphere product in the silica tube cools to 20 ℃ ± 2 ℃ with the furnace under argon shield;
9. close the argon gas valve, stop defeated argon gas;
10. take out silica tube, collect the carbosphere product on the quartzy tube wall;
(3) grind, sieve, purifying, thinning processing carbosphere
The carbosphere product is ground with agate mortar, sieve, grind, sieving repeats, retain the carbosphere fine powder with 650 eye mesh screens;
(4) oxide treatment carbosphere
1. the oxide treatment carbosphere stirs on the ware at there-necked flask, cleansing bath tub, electric heating and carries out, and under nitrogen protection, water cycle condensing state, accomplishes;
2. carbosphere 1g is added in the there-necked flask by addition funnel;
With potassium permanganate 0.5g+ deionized water 32mL, be mixed with 0.1mol/L solution, add in the there-necked flask by addition funnel;
Sulfuric acid 20ml is added in the there-necked flask by addition funnel;
3. open water inlet pipe, the rising pipe of water cycle prolong, carry out the water cycle condensation;
4. open nitrogen valve, nitrogengas cylinder, to there-necked flask input nitrogen, input speed 50cm
3/ min;
5. open electric heating and stir ware, temperature rises to 80 ℃ ± 2 ℃ by 20 ℃, and begins to stir, and carries out oxidizing reaction;
6. stir, oxidization time 360min ± 2min becomes: oxide soln;
7. in the carbosphere oxidising process, will carry out chemical reaction, reaction formula is following:
In the formula:
C-OH: hydroxyl carbosphere
MnO
2: Manganse Dioxide
K
2SO
4: vitriolate of tartar
8. after the oxidizing reaction, close electric heating and stir ware, make there-necked flask and interior oxide soln thereof be cooled to 20 ℃ ± 2 ℃ with cleansing bath tub;
9. suction filtration
Oxide soln is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper; Retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
10. the pH value is controlled in deionized water wash, suction filtration, measurement
The product filter cake is placed beaker, add deionized water 200ml, use the whisking appliance agitator treating;
Then washings is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
Deionized water wash, suction filtration repeat ten times;
In washing suction filtration process, measure the oxide soln potential of hydrogen, be neutral, the pH value is 7;
Washing gets the product filter cake behind the suction filtration;
Place vacuum drying oven to carry out drying treatment the product filter cake, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness 10Pa, time of drying, 480min got after the drying: the carbonoxide microballoon;
The carbonoxide microballoon is placed beaker, add oxalic acid 200ml, wash, stir 30min, on walls of beaker, have great amount of bubbles to emerge, become: washing soln;
Washing soln is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper, the product filter cake is retained on the filter paper, and waste liquid is evacuated in the filter flask;
Carbonoxide microballoon after the washing is placed beaker, add deionized water 300ml, agitator treating carries out suction filtration with three layers of middling speed qualitative filter paper then;
Washing, suction filtration repeat ten times;
In washing suction filtration process, measure solution acid alkalinity, be neutral, the pH value is 7;
Place vacuum drying oven to carry out vacuum-drying the carbonoxide microballoon of washing behind the suction filtration, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness is 10Pa, time of drying 480min;
After the drying: carbonoxide microballoon, i.e. hydroxylation carbosphere;
(5) modification carbosphere
1. the modification carbosphere stirs on the ware at there-necked flask, cleansing bath tub, electric heating and carries out, and under nitrogen protection, water cycle condensing state, accomplishes;
2. the carbonoxide microballoon is added in the there-necked flask;
Absolute ethyl alcohol 100ml is added in the there-necked flask;
Deionized water 100ml is added in the there-necked flask;
Properties-correcting agent γ-(methacryloxypropyl) propyl trimethoxy silicane 10ml is placed there-necked flask;
3. open water inlet pipe, the rising pipe of water cycle prolong, carry out the water cycle condensation;
4. open nitrogen valve, nitrogengas cylinder, input nitrogen, nitrogen input speed 50cm
3/ min;
5. open electric heating and stir ware, temperature rises to 55 ℃ ± 2 ℃ by 20 ℃, and stirs;
6. heated and stirred 840min ± 2min carries out the modification reaction;
7. in the modification reaction, chemical reaction will take place, reaction formula is following:
In the formula:
C-OH: hydroxyl carbosphere
C-C
9H
17O
5Si: the carbosphere of silylanization
8. behind modification, the modified-reaction, close electric heating and stir ware, stop heated and stirred, make it under nitrogen, water cycle condensing state, be cooled to 20 ℃ ± 2 ℃; : modification solution;
9. suction filtration
Modification solution is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
10. vacuum-drying
Place vacuum drying oven to carry out drying the product filter cake, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness 10pa, time of drying 480min ± 2min;
After the drying: the modification carbosphere;
(6) preparation trace carbosphere
1. prepare the trace carbosphere and on there-necked flask, electric heating stirring ware, cleansing bath tub, carry out, under nitrogen protection, water cycle condensation, accomplish;
2. the modification carbosphere is added in the there-necked flask, dibenzothiophene 0.369g is added in the there-necked flask, chloroform 20ml is added in the there-necked flask, α-Jia Jibingxisuan 1ml is added in the there-necked flask;
3. open the water inlet pipe rising pipe of water cycle prolong, carry out the water cycle condensation;
Open nitrogen valve, nitrogengas cylinder, input nitrogen, nitrogen input speed 50cm
3/ min;
Open electric heating and stir ware, make temperature rise to 60 ℃ ± 2 ℃, and begin to stir by 20 ℃;
4. evenly stir 30min ± 2min, modification carbosphere and dibenzothiophene, α-Jia Jibingxisuan are fully acted on;
5. add initiator Diisopropyl azodicarboxylate 0.065g, add linking agent TGM 1 4ml, continue to stir 1440min, and react;
6. in preparation trace carbosphere process, chemical reaction will take place, reaction formula is following:
In the formula:
C-C
35H
45O
11SSi: the trace carbosphere that contains dibenzothiophene
7. after the reaction, close electric heating and stir ware, make there-necked flask in cleansing bath tub, under nitrogen protection, under the water cycle condensation, naturally cool to 20 ℃ ± 2 ℃, become: trace carbosphere reaction soln;
8. suction filtration
Trace carbosphere reaction soln is placed the B of filter flask, carry out suction filtration with three layers of middling speed qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
9. absolute ethanol washing, suction filtration
Product filter cake behind the suction filtration is placed beaker, add absolute ethyl alcohol 100ml, agitator treating carries out suction filtration with three layers of middling speed qualitative filter paper then;
Washing, suction filtration repeat ten times;
10. methyl alcohol+glacial acetic acid washing, suction filtration, remove dibenzothiophene
Compounding methanol+glacial acetic acid mixing solutions
With methyl alcohol 720ml, glacial acetic acid 80ml places beaker, stirs 10min, becomes: mixing solutions;
The trace carbosphere is placed the mixing solutions in the beaker, use the whisking appliance agitator treating;
On filter flask, carry out suction filtration then with three layers of middling speed qualitative filter paper;
Washing, suction filtration repeat ten times;
Remove dibenzothiophene after the washing, form the hole, after the washing: the trace carbosphere;
The trace carbosphere is placed beaker, add absolute ethyl alcohol 100ml, agitator treating;
On filter flask, carry out suction filtration then with three layers of middling speed qualitative filter paper;
Washing, suction filtration repeat ten times;
Remove methyl alcohol, glacial acetic acid after the washing, get final product: trace carbosphere filter cake;
Place vacuum drying oven dry washing, final product carbosphere filter cake behind the suction filtration, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness 10Pa, time of drying 480min ± 2min;
Get final product after the drying: the trace carbosphere; That is: black powder trace carbosphere;
(7) detect, chemically examine, analyze, characterize
Color and luster, pattern, structure, composition, chemical physics performance, absorbancy, the concentration of trace carbosphere to preparation detects, analyzes, characterizes;
Carry out morphology analysis with field emission scanning electron microscope;
Carry out thermal stability analysis with thermogravimetric analyzer;
Carry out the surface functional group analysis with IR;
Carry out absorbance measuring with ultraviolet spectrophotometer;
Conclusion: the trace carbosphere is the black powder granule, and particle diameter is 100-200nm, and the carbosphere surface is irregular hollow cavity shaped;
(8) product stores
Airtight being stored in the water white Glass Containers of trace carbosphere product to preparation places drying, clean environment, waterproof, sun-proof, moistureproof, acid-proof alkali salt erosion, 20 ℃ ± 2 ℃ of storing temps, relative humidity≤10%.
2. the preparation method of a kind of molecular imprinted polymer on surface of carbon microspheres according to claim 1; It is characterized in that: the preparation of described trace carbosphere; Be be the carbon raw material with the acetylene gas, be carrier gas and shielding gas with the argon gas; With potassium permanganate, sulfuric acid is oxygenant, is washing composition with absolute ethyl alcohol, methyl alcohol, oxalic acid, glacial acetic acid, deionized water; Be shielding gas with nitrogen, be properties-correcting agent with γ-(methacryloxypropyl) propyl trimethoxy silicane; Be linking agent with the TGM 1, be initiator, be solvent, be trace carbosphere hole template with the dibenzothiophene with the chloroform with the Diisopropyl azodicarboxylate.
3. the preparation method of a kind of molecular imprinted polymer on surface of carbon microspheres according to claim 1; It is characterized in that: described trace carbosphere; Be black, circle, powder, particulate state, particle diameter is 100-200nm, and the trace on the particle is irregular hole distribution.
4. the preparation method of a kind of molecular imprinted polymer on surface of carbon microspheres according to claim 1; It is characterized in that: the preparation of described carbosphere, in tube type high-temperature furnace, carry out, its preparation state is: on High Temperature Furnaces Heating Apparatus (1) top is resistance heater (2); High Temperature Furnaces Heating Apparatus (1) inner bottom part is track (4); And connect track unit (5), and to go up at track (4) and put silica tube (3), silica tube (3) stretches in the High Temperature Furnaces Heating Apparatus on track (4); Silica tube (3) left part is provided with plug (17), plug (17) top UNICOM acetylene hose (8), acetylene valve (7), acetylene cylinder (6), bottom UNICOM tunger tube (11), argon gas valve (10), argon bottle (9); Silica tube (3) right part is provided with plug (18), and parallelly connected pass-out tracheae (16), the interior left part of silica tube (3) are that low temperature section (12), right part are that low temperature section (14), middle part are high temperature section (13), are carbosphere product (15) on high temperature section (13) tube wall.
5. the preparation method of a kind of molecular imprinted polymer on surface of carbon microspheres according to claim 1; It is characterized in that: the preparation of described trace carbosphere, its oxidation, modification, trace moulding are all carried out in there-necked flask, and its preparation state is: there-necked flask (23) places on the cleansing bath tub (22); Cleansing bath tub (22) places electric heating to stir on the ware (21); Electric heating stirs ware (21) and is provided with image display (24), PL (25), trip switch (26); Be water-bath water (36) in the cleansing bath tub (22); There-necked flask (23) top is provided with nitrogen tube (29), addition funnel (30), water cycle prolong (31); Nitrogen tube (29) connects nitrogen valve (28), nitrogengas cylinder (27); Water cycle prolong (31) connects water inlet pipe (33), rising pipe (34); Top is production well (32); There-necked flask (23) inner bottom part is carbosphere (37), mixing solutions (38), and top is nitrogen (35).
6. the preparation method of a kind of molecular imprinted polymer on surface of carbon microspheres according to claim 1 is characterized in that: the moulding preparation of described trace carbosphere, completion under anhydrous state.
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| CN102977290A (en) * | 2012-12-11 | 2013-03-20 | 太原理工大学 | Method for preparing imprinted carbon microsphere by ultrasonic assistance |
| CN103332671B (en) * | 2013-06-18 | 2015-08-12 | 太原理工大学 | A kind of preparation method of porous trace Nano carbon balls |
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| CN1962428A (en) * | 2005-11-10 | 2007-05-16 | 鸿富锦精密工业（深圳）有限公司 | Nanometer carbon tube modification process |
| CN101318660A (en) * | 2008-07-12 | 2008-12-10 | 太原理工大学 | Method of preparing hollow silicon dioxide ball |
| CN101524636A (en) * | 2009-04-10 | 2009-09-09 | 南京医科大学 | Method for preparing bisphenol A nanometer silicon gel carrier surface molecule print solid phase extraction filling |
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| CN1962428A (en) * | 2005-11-10 | 2007-05-16 | 鸿富锦精密工业（深圳）有限公司 | Nanometer carbon tube modification process |
| CN101318660A (en) * | 2008-07-12 | 2008-12-10 | 太原理工大学 | Method of preparing hollow silicon dioxide ball |
| CN101524636A (en) * | 2009-04-10 | 2009-09-09 | 南京医科大学 | Method for preparing bisphenol A nanometer silicon gel carrier surface molecule print solid phase extraction filling |
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