CN104072693A - Method for preparing thermosensitive polymer-grafted carbon ball compound - Google Patents
Method for preparing thermosensitive polymer-grafted carbon ball compound Download PDFInfo
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- CN104072693A CN104072693A CN201410326972.XA CN201410326972A CN104072693A CN 104072693 A CN104072693 A CN 104072693A CN 201410326972 A CN201410326972 A CN 201410326972A CN 104072693 A CN104072693 A CN 104072693A
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- necked flask
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Abstract
The invention relates to a method for preparing a thermosensitive polymer-grafted carbon ball compound. According to the method, aiming at the defects of chemical and physical properties existing in the carbon ball of the carbon material, oxidization modification is carried out on the carbon ball surface to prepare a vinyl functionalized carbon ball, and then thermosensitive polymer grafting is carried out on the carbon ball, so as to prepare the thermosensitive carbon ball compound. The preparation method is advanced in process, and accurate and detailed in data, the prepared product is black spherical powder particle, the diameter of the particle is smaller than or equal to 400nm, the purity of the product can be up to 98%, the phase inversion temperature of the compound is 39 DEG C, the compound can be matched with a plurality of chemical substances, the serviceable range of the carbon ball of the carbon material is expanded, and the method is an ideal method for preparing the thermosensitive polymer-grafted carbon ball compound.
Description
Technical field
The present invention relates to a kind of preparation method of temperature sensing polymer grafting carbon ball mixture, belong to the technical field of carbon material preparation, Thermo-sensitive modification and application.
Background technology
Organic-inorganic composition is a kind of functional composite material, stimulating responsive composite organic-inorganic material, greatly improve the performance of matrix material, the physical and chemical performance of mixture can regulate to meet different application demands by ambient conditions, for example drug conveying, biological nano technology, sensor; In stimulating responsive polymer, temperature-responsive polymkeric substance in biomedical sector application at most, can utilize the subtle change of human body temperature to make drug release; Poly N-isopropyl acrylamide is temperature sensitive polymer, and the lowest critical solution temperature while occurring to change mutually in the aqueous solution is 32 DEG C.When temperature is during lower than 32 DEG C, between the amide group in polymkeric substance and aqueous solvent, form hydrogen bond, polymkeric substance is wetting ability; When temperature is during higher than 32 DEG C, due to hydrogen bond rupture between amide group in polymkeric substance and aqueous solvent, polymkeric substance is hydrophobicity; Therefore poly N-isopropyl acrylamide is applied to biomedical sector to the response performance of temperature, the absorption of for example protein and purifying, drug conveying, catalytic field.Poly N-isopropyl acrylamide also can the multiple matrix of grafting, synthetic Thermo-sensitive matrix material.
Carbon ball is most important carbon material, and physical and chemical performance is superior, has chemical stability, thermostability, excellent machinability and electrical and thermal conductivity, can make the multiple matrix material such as anode material, sorbent material, electrochemical electrode, carbon film of lithium cell; In order to improve the range of application of carbon ball, often to carbon ball modifying surface and functionalization, so that carbon ball surface increases oxygen-containing functional group, as carboxyl, hydroxyl and carbonyl, make double bond containing organism be attached to carbon ball surface, obtain carbon sphere/polymer matrix material, to improve the range of application of carbon ball.
Summary of the invention
Goal of the invention
The object of the invention is the situation for background technology, taking carbon ball as raw material, carbon ball is carried out to silanization processing, grafting temperature sensing polymer poly N-isopropyl acrylamide, make Thermo-sensitive carbon ball mixture, to change the chemical physics performance of carbon ball, expand the use range of carbon ball.
Technical scheme
The chemical substance material that the present invention uses is: carbon ball, NIPA, N, N-methylene diacrylamine, ammonium persulphate, sulfuric acid, nitric acid, γ-(methacryloxypropyl) propyl trimethoxy silicane, dehydrated alcohol, deionized water, nitrogen, it is as follows that it prepares consumption: with gram, milliliter, centimetre
3for measure unit
γ-(methacryloxypropyl) propyl trimethoxy silicane:
Preparation method is as follows:
(1) carbon ball surface oxidation modification
1. prepare mixed acid solution
Measure sulfuric acid 90mL ± 1mL, nitric acid 30mL ± 1mL, be placed in beaker, be uniformly mixed 2min, become mixed acid solution;
2. ultrasonic dispersion, oxidation modification
Carbon ball 1g ± 0.001g is placed in to beaker, adds mixed acid solution 120mL ± 1mL, then beaker is placed in to ultrasonic separating apparatus, carry out ultrasonic dispersion, ultrasonic frequency 40KHz, ultrasonic jitter time 30min, becomes carbon ball mixed solution; Then beaker is moved in water bath with thermostatic control heating magnetic stirring apparatus, at 80 DEG C, continue stirring reaction 20min;
3. suction filtration
The carbon ball mixed solution of oxidation modification is placed in to the Büchner funnel of filter flask, carries out suction filtration with millipore filtration, retain product filter cake on filter membrane, waste liquid is evacuated in filter flask;
4. washing, suction filtration
Product filter cake is placed in to beaker, adds deionized water 50mL, agitator treating 5min, then suction filtration on filter flask;
Washing, suction filtration repeat three times;
5. vacuum-drying
Product filter cake is placed in to quartz container, is then placed in loft drier dry, 80 DEG C of drying temperatures, vacuum tightness 0.09MPa, time of drying, 720min, was carbonoxide ball C-OH after being dried;
(2) prepare vinyl functionalized carbon ball
1. prepare γ-(methacryloxypropyl) propyl trimethoxy silicane aqueous solution
Measure γ-(methacryloxypropyl) propyl trimethoxy silicane 1.5mL ± 0.01mL, deionized water 40mL ± 1mL, add in beaker, stir 5min, become γ-(methacryloxypropyl) propyl trimethoxy silicane aqueous solution of 0.1671mol/L;
2. take oxidation modification carbon ball 0.5g ± 0.001g, measure dehydrated alcohol 50mL ± 1mL, deionized water 30mL ± 1mL, add in there-necked flask, stir 5min, become mixed solution;
3. the there-necked flask that fills mixed solution is placed on ultrasonic separating apparatus to ultrasonic dispersion treatment 30min, ultrasonic frequency 40KHz;
4. the there-necked flask that fills mixed solution is put into water-bath magnetic stirring apparatus, 60 DEG C ± 2 DEG C of Heating temperatures, stir, drip γ-(methacryloxypropyl) propyl trimethoxy silicane aqueous solution, rate of addition 1.5mL/min, time for adding 26min, after dropping, stirring reaction 240min;
Drip in whipping process generating functionization is reacted, reaction formula is as follows:
In formula: C-OH: carbonoxide ball
C
10h
17o
5si: vinyl functionalized carbon ball
CH
3oH: methyl alcohol
5. suction filtration, is placed in the mixed solution after reaction kinetic the Büchner funnel of filter flask, carries out suction filtration with millipore filtration, retains product filter cake, and waste liquid is evacuated in filter flask;
6. washing, suction filtration, be placed in beaker by product filter cake, adds dehydrated alcohol 30mL, agitator treating 5min; Then carry out suction filtration with millipore filtration, after suction filtration, obtain product filter cake;
Absolute ethanol washing, suction filtration repeat three times;
7. vacuum-drying, is placed in quartz container by the filter cake after suction filtration, is then placed in vacuum drying oven dry, 60 DEG C of drying temperatures, and vacuum tightness 0.09MPa, time of drying, 720min, became vinyl functionalized carbon ball after being dried;
(3) prepare temperature sensing polymer grafting carbon ball mixture
Temperature sensing polymer grafting carbon ball mixture carries out in there-necked flask, under water-bath, heating, nitrogen protection, completes;
1. prepare ammonium persulfate aqueous solution, take ammonium persulphate 0.009g ± 0.001g, measure deionized water 5mL ± 0.1mL, add in beaker, stir 5min, become 0.0000394mol/L ammonium persulfate aqueous solution;
2. take vinyl functionalized carbon ball 0.3g ± 0.001g, add in there-necked flask, add deionized water 45mL ± 1mL, be then placed on cleansing bath tub, dispersed with stirring under water-bath state, time 40min, becomes mixed solution;
Then add monomer NIPA 0.9g ± 0.001g, linking agent N, N-methylene diacrylamine 0.135g ± 0.001g; Then to there-necked flask input nitrogen, nitrogen input speed 100cm
3/ min; Magneton agitator stirs, time 15min; Then heater, heats, 70 DEG C ± 1 DEG C of Heating temperature;
By the initiator ammonium persulfate aqueous solution 5mL ± 0.01mL of preparation, in syringe injection there-necked flask, continue to react 240min under heating, nitrogen protection;
After ultrasonic dispersion, become carbon ball mixture mixed solution;
In preparation process, combination reaction will occur, reaction formula is as follows:
In formula: C
16h
28o
6siN: temperature sensing polymer grafting carbon ball mixture
3. centrifugation, is placed in carbon ball mixture mixed solution in centrifugal separating tube, carries out centrifugation, separates rotating speed 6000r/min, disengaging time 10min; Collecting precipitation thing after separating, abandoning supernatant;
4. deionized water wash, suction filtration
Throw out is placed in to beaker, adds deionized water 50mL, agitator treating 5min;
Then carry out suction filtration with millipore filtration, retain product filter cake; Washing, suction filtration repeat five times;
5. vacuum-drying, is placed in quartz container by the product filter cake after washing, suction filtration, is then placed in vacuum drying oven dry; 80 DEG C of drying temperatures, vacuum tightness 0.09MPa, time of drying, 720min, was temperature sensing polymer grafting carbon ball mixture after being dried;
(4) detect, analyze, characterize
Pattern, color and luster, the chemical physics performance of the temperature sensing polymer grafting carbon ball mixture to preparation detect, analyze, characterize;
Carry out morphology analysis with field emission scanning electron microscope;
Carry out the analysis of surface grafting polymerization thing with infrared spectrometer;
Conclusion: temperature sensing polymer grafting carbon ball mixture is the spherical powder granule of black, particle diameter≤400nm, product purity 98%, mixture phase transition temperature is 39 DEG C;
(5) product stores
Temperature sensing polymer grafting carbon ball mixture powder granule to preparation is stored in brown transparent Glass Containers, and airtight keeping in Dark Place wants waterproof, sun-proof, anti-acid-alkali salt to corrode, 20 DEG C of storing temps, relative humidity≤10%.
Beneficial effect
The present invention has obvious advance compared with background technology, it is the deficiency for the chemical physics performance of carbon material carbon ball existence, through carbon ball is carried out to Surface Oxidation Modification, make vinyl functionalized carbon ball, again carbon ball is carried out to temperature sensing polymer grafting, make Thermo-sensitive carbon ball mixture, this preparation method's technique advanced person, data are accurately full and accurate, the product of making is the spherical powder granule of black, particle diameter≤400nm, product purity reaches 98%, mixture phase transition temperature is 39 DEG C, can mate with number of chemical material, expand the use range of carbon material carbon ball, it is the very good method of preparing temperature sensing polymer grafting carbon ball mixture.
Brief description of the drawings
Fig. 1, prepares the state graph of temperature sensing polymer grafting carbon ball mixture
Fig. 2, temperature sensing polymer grafting carbon ball mixture shape appearance figure
Fig. 3, temperature sensing polymer grafting carbon ball mixture infrared spectrogram
Fig. 4, the temperature variant graphic representation of hydration kinetics diameter of temperature sensing polymer grafting carbon ball mixture
Shown in figure, list of numerals is as follows:
1, electric control box, 2, cleansing bath tub, 3, there-necked flask, 4, water-bath water, 5, anchor, 6, inlet pipe, 7, dropping funnel, 8, control valve, 9, water cycle prolong, 10, water-in, 11, water outlet, 12, air outlet, 13, nitrogengas cylinder, 14, nitrogen tube, 15, nitrogen valve, 16, display screen, 17, pilot lamp, 18, power switch, 19, heating and temperature control device, 20, heat-up time controller, 21, magneton agitator, 22, carbon ball mixture mixed solution, 23, nitrogen.
Embodiment
Below in conjunction with accompanying drawing, the present invention will be further described:
Shown in Fig. 1, for preparing the state graph of temperature sensing polymer grafting carbon ball mixture, it is correct that want each portion position, proportioning according to quantity, according to the order of sequence operation.
The value of the chemical substance that preparation is used is to determine by the scope setting in advance, with gram, milliliter, centimetre
3for measure unit.
Temperature sensing polymer grafting carbon ball mixture carries out in there-necked flask, under water-bath, heating, nitrogen protection, completes;
Cleansing bath tub is vertical, is electric control box 1 in the bottom of cleansing bath tub 2, is there-necked flask 3 on the top of cleansing bath tub 2, and is fixed by anchor 5, in cleansing bath tub 2, is water-bath water 4, and water-bath water 4 will flood 4/5 of there-necked flask volume; On there-necked flask 3 tops, inlet pipe 6, dropping funnel 7 and control valve 8, water cycle prolong 9 and water-in 10, water outlet 11, air outlet 12 are set from left to right, there-necked flask 3 inner bottom parts are provided with magneton agitator 21, in there-necked flask, are carbon ball mixture mixed solution 22, nitrogen tube 23; Be provided with nitrogengas cylinder 13 at cleansing bath tub 2 left parts, nitrogengas cylinder 13 tops connect nitrogen tube 14, nitrogen valve 15, and pass through inlet pipe 6 to the interior input nitrogen 23 of there-necked flask 3; On electric control box 1, be provided with display screen 16, pilot lamp 17, power switch 18, heating and temperature control device 19, heat-up time controller 20.
Shown in Fig. 2, be temperature sensing polymer grafting carbon ball mixture shape appearance figure, as shown in the figure, carbon ball mixture is spherical powder particle, and particle diameter≤400nm, is irregular stacking, and diameter increases explanation temperature sensing polymer and is grafted to carbon ball surface.
Shown in Fig. 3, be temperature sensing polymer grafting carbon ball mixture infrared spectrogram, as seen from the figure, in the spectrogram of the carbon ball after graft N-N-isopropylacrylamide at 1641cm
-1and 1539cm
-1there are two new absorption peaks in place, this is C ═ O (acid amides I) and N-H (acid amides II) the stretching vibration absorption peak of amide group in NIPA molecule; Be positioned at 1370cm
-1the characteristic absorption band at place is C-H stretching vibration generation on sec.-propyl in NIPA molecule, is positioned at 2870cm
-1and 2970cm
-1the absorption peak at place belongs to the flexible of methylene radical and flexural vibration absorption generation; At 3200～3400cm
-1locate the N-H stretching vibration that wide absorption band derives from acid amides.
Shown in Fig. 4, for the temperature variant graphic representation of hydration kinetics diameter of temperature sensing polymer grafting carbon ball mixture, as seen from the figure, along with the rising of temperature, the hydration kinetics diameter of mixture microballoon reduces gradually, illustrates that mixture has temperature-responsive, in the time that temperature is elevated to 52 DEG C from 25 DEG C, diameter drops to 471nm from 585nm, occurs obvious particle diameter sudden change at about 39 DEG C, and mixture phase transition temperature is 39 DEG C.
Claims (2)
1. the preparation method of a temperature sensing polymer grafting carbon ball mixture, it is characterized in that: the chemical substance material of use is: carbon ball, NIPA, N, N-methylene diacrylamine, ammonium persulphate, sulfuric acid, nitric acid, γ-(methacryloxypropyl) propyl trimethoxy silicane, dehydrated alcohol, deionized water, nitrogen, it is as follows that it prepares consumption: with gram, milliliter, centimetre
3for measure unit
γ-(methacryloxypropyl) propyl trimethoxy silicane:
Preparation method is as follows:
(1) carbon ball surface oxidation modification
1. prepare mixed acid solution
Measure sulfuric acid 90mL ± 1mL, nitric acid 30mL ± 1mL, be placed in beaker, be uniformly mixed 2min, become mixed acid solution;
2. ultrasonic dispersion, oxidation modification
Carbon ball 1g ± 0.001g is placed in to beaker, adds mixed acid solution 120mL ± 1mL, then beaker is placed in to ultrasonic separating apparatus, carry out ultrasonic dispersion, ultrasonic frequency 40KHz, ultrasonic jitter time 30min, becomes carbon ball mixed solution; Then beaker is moved in water bath with thermostatic control heating magnetic stirring apparatus, at 80 DEG C, continue stirring reaction 20min;
3. suction filtration
The carbon ball mixed solution of oxidation modification is placed in to the Büchner funnel of filter flask, carries out suction filtration with millipore filtration, retain product filter cake on filter membrane, waste liquid is evacuated in filter flask;
4. washing, suction filtration
Product filter cake is placed in to beaker, adds deionized water 50mL, agitator treating 5min, then suction filtration on filter flask;
Washing, suction filtration repeat three times;
5. vacuum-drying
Product filter cake is placed in to quartz container, is then placed in loft drier dry, 80 DEG C of drying temperatures, vacuum tightness 0.09MPa, time of drying, 720min, was carbonoxide ball C-OH after being dried;
(2) prepare vinyl functionalized carbon ball
1. prepare γ-(methacryloxypropyl) propyl trimethoxy silicane aqueous solution
Measure γ-(methacryloxypropyl) propyl trimethoxy silicane 1.5mL ± 0.01mL, deionized water 40mL ± 1mL, add in beaker, stir 5min, become γ-(methacryloxypropyl) propyl trimethoxy silicane aqueous solution of 0.1671mol/L;
2. take oxidation modification carbon ball 0.5g ± 0.001g, measure dehydrated alcohol 50mL ± 1mL, deionized water 30mL ± 1mL, add in there-necked flask, stir 5min, become mixed solution;
3. the there-necked flask that fills mixed solution is placed on ultrasonic separating apparatus to ultrasonic dispersion treatment 30min, ultrasonic frequency 40KHz;
4. the there-necked flask that fills mixed solution is put into water-bath magnetic stirring apparatus, 60 DEG C ± 2 DEG C of Heating temperatures, stir, drip γ-(methacryloxypropyl) propyl trimethoxy silicane aqueous solution, rate of addition 1.5mL/min, time for adding 26min, after dropping, stirring reaction 240min;
Drip in whipping process generating functionization is reacted, reaction formula is as follows:
In formula: C-OH: carbonoxide ball
C
10h
17o
5si: vinyl functionalized carbon ball
CH
3oH: methyl alcohol
5. suction filtration, is placed in the mixed solution after reaction kinetic the Büchner funnel of filter flask, carries out suction filtration with millipore filtration, retains product filter cake, and waste liquid is evacuated in filter flask;
6. washing, suction filtration, be placed in beaker by product filter cake, adds dehydrated alcohol 30mL, agitator treating 5min; Then carry out suction filtration with millipore filtration, after suction filtration, obtain product filter cake;
Absolute ethanol washing, suction filtration repeat three times;
7. vacuum-drying, is placed in quartz container by the filter cake after suction filtration, is then placed in vacuum drying oven dry, 60 DEG C of drying temperatures, and vacuum tightness 0.09MPa, time of drying, 720min, became vinyl functionalized carbon ball after being dried;
(3) prepare temperature sensing polymer grafting carbon ball mixture
Temperature sensing polymer grafting carbon ball mixture carries out in there-necked flask, under water-bath, heating, nitrogen protection, completes;
1. prepare ammonium persulfate aqueous solution, take ammonium persulphate 0.009g ± 0.001g, measure deionized water 5mL ± 0.1mL, add in beaker, stir 5min, become 0.0000394mol/L ammonium persulfate aqueous solution;
2. take vinyl functionalized carbon ball 0.3g ± 0.001g, add in there-necked flask, add deionized water 45mL ± 1mL, be then placed on cleansing bath tub, dispersed with stirring under water-bath state, time 40min, becomes mixed solution;
Then add monomer NIPA 0.9g ± 0.001g, linking agent N, N-methylene diacrylamine 0.135g ± 0.001g; Then to there-necked flask input nitrogen, nitrogen input speed 100cm
3/ min; Magneton agitator stirs, time 15min; Then heater, heats, 70 DEG C ± 1 DEG C of Heating temperature;
By the initiator ammonium persulfate aqueous solution 5mL ± 0.01mL of preparation, in syringe injection there-necked flask, continue to react 240min under heating, nitrogen protection;
After ultrasonic dispersion, become carbon ball mixture mixed solution;
In preparation process, combination reaction will occur, reaction formula is as follows:
In formula: C
16h
28o
6siN: temperature sensing polymer grafting carbon ball mixture
3. centrifugation, is placed in carbon ball mixture mixed solution in centrifugal separating tube, carries out centrifugation, separates rotating speed 6000r/min, disengaging time 10min; Collecting precipitation thing after separating, abandoning supernatant;
4. deionized water wash, suction filtration
Throw out is placed in to beaker, adds deionized water 50mL, agitator treating 5min;
Then carry out suction filtration with millipore filtration, retain product filter cake; Washing, suction filtration repeat five times;
5. vacuum-drying, is placed in quartz container by the product filter cake after washing, suction filtration, is then placed in vacuum drying oven dry; 80 DEG C of drying temperatures, vacuum tightness 0.09MPa, time of drying, 720min, was temperature sensing polymer grafting carbon ball mixture after being dried;
(4) detect, analyze, characterize
Pattern, color and luster, the chemical physics performance of the temperature sensing polymer grafting carbon ball mixture to preparation detect, analyze, characterize;
Carry out morphology analysis with field emission scanning electron microscope;
Carry out the analysis of surface grafting polymerization thing with infrared spectrometer;
Conclusion: temperature sensing polymer grafting carbon ball mixture is the spherical powder granule of black, particle diameter≤400nm, product purity 98%, mixture phase transition temperature is 39 DEG C;
(5) product stores
Temperature sensing polymer grafting carbon ball mixture powder granule to preparation is stored in brown transparent Glass Containers, and airtight keeping in Dark Place wants waterproof, sun-proof, anti-acid-alkali salt to corrode, 20 DEG C of storing temps, relative humidity≤10%.
2. the preparation method of a kind of temperature sensing polymer grafting carbon ball mixture according to claim 1, is characterized in that: temperature sensing polymer grafting carbon ball mixture carries out in there-necked flask, under water-bath, heating, nitrogen protection, completes;
Cleansing bath tub is vertical, be electric control box (1) in the bottom of cleansing bath tub (2), be there-necked flask (3) on the top of cleansing bath tub (2), and fixing by anchor (5), in cleansing bath tub (2), be water-bath water (4), water-bath water (4) will flood 4/5 of there-necked flask volume; On there-necked flask (3) top, inlet pipe (6), dropping funnel (7) and control valve (8), water cycle prolong (9) and water-in (10), water outlet (11), air outlet (12) are set from left to right, there-necked flask (3) inner bottom part is provided with magneton agitator (21), in there-necked flask, is carbon ball mixture mixed solution (22), nitrogen tube (23); Be provided with nitrogengas cylinder (13) at cleansing bath tub (2) left part, nitrogengas cylinder (13) top connects nitrogen tube (14), nitrogen valve (15), and in there-necked flask (3), inputs nitrogen (23) by inlet pipe (6); On electric control box (1), be provided with display screen (16), pilot lamp (17), power switch (18), heating and temperature control device (19), controller heat-up time (20).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107032324A (en) * | 2017-03-23 | 2017-08-11 | 太原理工大学 | A kind of preparation method of the order mesoporous Nano carbon balls of magnetic for target administration |
| CN116407646A (en) * | 2021-12-30 | 2023-07-11 | 中南民族大学 | Preparation method and application of dual-carrier dual-drug temperature response type drug delivery system |
| CN116407646B (en) * | 2021-12-30 | 2024-05-31 | 中南民族大学 | Preparation method and application of dual-carrier dual-drug temperature response type drug delivery system |
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|---|---|---|---|---|
| US3937775A (en) * | 1972-10-23 | 1976-02-10 | Sumitomo Chemical Company, Limited | Process for production of carbon products |
| CN102720053A (en) * | 2012-06-18 | 2012-10-10 | 太原理工大学 | Flame-retardant treatment method for wool fibers |
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2014
- 2014-07-10 CN CN201410326972.XA patent/CN104072693B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3937775A (en) * | 1972-10-23 | 1976-02-10 | Sumitomo Chemical Company, Limited | Process for production of carbon products |
| CN102720053A (en) * | 2012-06-18 | 2012-10-10 | 太原理工大学 | Flame-retardant treatment method for wool fibers |
Non-Patent Citations (2)
| Title |
|---|
| LIN CHEN ET AL: "Preparation and characterization of thermosensitive core/shell microgels with carbon microsphere cores", 《JOURNAL OF MATERIALS RESEARCH》, vol. 29, no. 10, 28 May 2014 (2014-05-28) * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107032324A (en) * | 2017-03-23 | 2017-08-11 | 太原理工大学 | A kind of preparation method of the order mesoporous Nano carbon balls of magnetic for target administration |
| CN107032324B (en) * | 2017-03-23 | 2019-01-15 | 太原理工大学 | A kind of preparation method of the order mesoporous Nano carbon balls of magnetism for target administration |
| CN116407646A (en) * | 2021-12-30 | 2023-07-11 | 中南民族大学 | Preparation method and application of dual-carrier dual-drug temperature response type drug delivery system |
| CN116407646B (en) * | 2021-12-30 | 2024-05-31 | 中南民族大学 | Preparation method and application of dual-carrier dual-drug temperature response type drug delivery system |
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