CN101125895A - Full-methylated cyclodextrinaniline nano supermolecule conducting polymer and its preparation method and use - Google Patents
Full-methylated cyclodextrinaniline nano supermolecule conducting polymer and its preparation method and use Download PDFInfo
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Abstract
The invention relates to a complete methylate cyclodextrin anilin nano supermolecule conducting polymer and the preparation method and application thereof. The invention is obtained from polymerization of complete methylate beta- cyclodextrin anilin clathrate in acid solution. The synthesis process of the invention is totally finished in aqueous phase and the whole process is easy and simple. The results of AFM and TEM experiment prove that the complete methylate cyclodextrin anilin nano supermolecule conducting polymer and the polyaniline both produced under the same condition are significantly different in aggregating form. Furthermore, compared with the polyaniline synthesized by the prior art, the water solubility of the invention is apparently improved, although condustance ratio is reduced, the trend of condustance ratio changing with temperature is different from polyaniline because the condustance ratio of the invention changes relatively small in a wider temperature range. The invention has a wide application prospect in the technological field of nano supermolecule materials.
Description
[technical field]
The invention belongs to nano-supermolecule material technology field, relate to full-methylated cyclodextrinaniline nano supermolecule conducting polymer and preparation method thereof.This invention has made water miscible full-methylated cyclodextrinaniline nano supermolecule conducting polymer by the inclusion compound of methylate beta-cyclodextrin and aniline at aqueous phase.This compound can be used as the nanoscale molecular lead with insulation layer, has broad application prospects in technical field of nano material.
[background technology]
Electric wire is the product that is seen everywhere in a kind of people's daily life.The copper wire of conduction superscribes one deck insulated shell promptly becomes our insulated conductor used in everyday.The insulating shell is generally plastics, and it mainly act as and reduces the loss of electric energy in transmittance process.The electricity discovery with make human society enter the brand-new epoch.With respect to the metallic conductor that generally uses, it is comparatively slow that the discovery of non-metal conductor and application seem.As far back as the forties in 20th century, the polyene hydrocarbon structural polymer can produce the general character of metalloid lead to scientists with regard to there's a widespread conviction that.To the sixties, the discovery of nitrogenize sulphur conducting polymer makes the research of molecular wire be subjected to paying close attention to more widely.Now, many polymers with conduction property are excavated successively, are used as photorectifier, transistor, and photocell and transmitter.The polymkeric substance of high conductivity is called as " molecular electric wire ".The lead of this molecular level is not macroscopic, and the sample on the macroscopic view can be thought the aggregate of a large amount of molecular wires.Therefore, for fear of the energy loss that the contact between these leads brings, insulation layer just seems important on the molecular wire external parcel.The discovery of super molecular complex has brought opportunity for the insulating of molecular wire.Development along with supramolecular chemistry, increasing big ring host compound is used to be wrapping on the catenate molecular wire, encircles acceptor and long-chain greatly to passing through hydrophobic interaction between body, and weak interaction forces such as electrostatic interaction form rotaxane, poly-rotaxane, the super molecular complex of forms such as pseudo-polyrotaxane.Chinese patent CN1850880A discloses with a spot of beta-cyclodextrin as dispersion agent, the method for the polyaniline conductive polymer that the preparation dispersity is higher.This also understands the existence such as non covalent bond effect between the big ring acceptor of cyclodextrin one class and the conducting high polymers thing on the other hand.
Beta-cyclodextrin be a class by α-1, the cyclic oligosaccharide that the 4-glycosidic link joins end to end and forms.As the good host compound of a class in the supramolecular chemistry, cyclodextrin and derivative thereof can form stable host-guest coordination compound with many organic molecules.Whole hydroxyls in the natural cyclodextrin promptly become permethylated beta-cyclodextrin after methylating.With respect to natural cyclodextrin, permethylated beta-cyclodextrin all has solubleness preferably in polarity and non-polar solvent, is subjected to the influence of pH value also less simultaneously.These characteristics make the permethylated beta-cyclodextrin can be as the good material of molecular wire insulation layer.
About the existing bibliographical information of the insulating molecule lead of cyclodextrin parcel, a series of poly-rotaxane title complexs have been reported at " Angew.Chem. " " Chem.Commun. " magazines such as " Chem.Eur.J " respectively from 2000 to 2004 based on beta-cyclodextrin as the Anderson scientific research group of Britain.As:
The synthetic metal catalyst that needs of these title complexs, synthetic condition are also relatively harsher.With respect to above polymkeric substance, polyaniline be a kind of be simple and easy to relatively structural conductive macromolecular, it is high that it has stability, the specific conductivity advantages of higher.About the first Ito experimental group that sees Japan of the high molecular report of cyclodextrin parcel polyaniline.1998, Ito and his co-worker joined beta-cyclodextrin in the N-methylpyrrole solution of polyaniline, had obtained the polyaniline pseudo-polyrotaxane of beta-cyclodextrin parcel under the low temperature.But this class is synthetic for solvent and temperature, and the condition of pH is than polyaniline some harshness that still seems itself, and can not directly obtain the super molecular complex of polyaniline and cyclodextrin under gentle relatively condition by the polymeric method.
[summary of the invention]
Purpose of the present invention aims to provide a kind of full-methylated cyclodextrinaniline nano supermolecule conducting polymer and preparation method thereof and purposes.The present invention is started with by permethylated beta-cyclodextrin aniline inclusion compound, obtained full-methylated cyclodextrinaniline nano supermolecule conducting polymer at the aqueous phase direct polymerization, overcome in the conventional art for the strictness restriction of solvent and pH value, prepared a kind of new electro-conductive material easily.
The invention discloses a kind of full-methylated cyclodextrinaniline nano supermolecule conducting polymer, it is characterized in that the inclusion compound polymerization in acidic aqueous solution that is made of permethylated beta-cyclodextrin and aniline obtains, its general structure is:
Described polymkeric substance is under the condition of pure water at dispersion agent, and its pattern yardstick is a nano level, and by the aggregate of a plurality of little spherical or similar wire that the ellipticity object is formed, under 25 ℃-100 ℃, its average conductivity is 1.53 * 10
-4-1.53 * 10
-4Sm
-1
The invention also discloses the preparation method of full-methylated cyclodextrinaniline nano supermolecule conducting polymer, it is characterized in that: the inclusion compound by described permethylated beta-cyclodextrin and aniline, in acidic aqueous solution, obtain, its synthesis step comprises:
(1) aniline is soluble in water fully, this aqueous solution is added in the aqueous solution of permethylated beta-cyclodextrin, aniline is 1 with the ratio of the amount of substance of permethylated beta-cyclodextrin: 0.5-2.0;
(2) mixed system at room temperature stirred 5-10 hour, will can obtain the micro-yellow powder of permethylated beta-cyclodextrin aniline inclusion compound behind the solvent evaporate to dryness;
(3) under the room temperature micro-yellow powder of permethylated beta-cyclodextrin aniline inclusion compound is dissolved in the acidic aqueous solution of 0.5-3.0M fully, stirs and add aqueous oxidizing agent solution down; Permethylated beta-cyclodextrin aniline inclusion compound is 1 with the ratio of the amount of substance of oxygenant: 0.25-2.0;
(4) mixed system at room temperature stirred 15-24 hour, then the blackish green precipitation of separating out in the system was collected, and with distilled water wash for several times, vacuum-drying obtains blackish green pulverulent solids polymkeric substance.
Full-methylated cyclodextrinaniline nano supermolecule conducting polymer can directly be obtained at the aqueous phase direct polymerization by the full-methylated cyclodextrinaniline inclusion compound among the present invention, simple synthetic method is easily gone, and has broad application prospects in nano-supermolecule material technology field.Its preparation method has overcome in the prior art for the strictness restriction of solvent and pH value, by the inclusion title complex of Subjective and Objective, has prepared a kind of nano-supermolecule conducting polymer with insulation layer easily.
The absorption band of polymkeric substance of the present invention in pure water appear at respectively about 690nm and 350nm (as Fig. 2, the ultraviolet-visible-near-infrared spectrum figure of supermolecule polymer in water and in the NaOH aqueous solution.Concentration: 0.01mmol dm
-3T=298K), in the 1M NaOH aqueous solution this compound immediately by the blackish green bluish voilet that becomes.Simultaneously blue shift all appears in two charge transfer absorption band, wherein the absorption band blue shift at 690nm place to about the 580nm, blue shift nearly 90nm.And the absorption band at 350nm place also has a little blue shift phenomenon, blue shift about 5nm.The result of spectrum experiment shows that this compound has and the simple similar character of molecular wire.With the ultraviolet comparison diagram (Fig. 3) of simple conducting polymer PANI in, we see with respect to simple PANI, two absorption bands of this compound all have some blue shift phenomenons, and this should be because the inclusion effect of permethylated beta-cyclodextrin causes the ratio rising of eigenstate PANI in whole polymkeric substance to cause.
Polymkeric substance is through 1H NMR, UV-vis-near IR, and IR etc. analyze the sign of means, and by AFM, means such as TEM have systematically been studied the grown form of this compound.Nanometer conductive polymer provided by the invention has certain conductive capability, and is water-soluble apparently higher than polyaniline.
[description of drawings]
Fig. 1: the synthetic route synoptic diagram of full-methylated cyclodextrinaniline nano supermolecule conducting polymer.
Fig. 2: the ultraviolet-visible-near-infrared spectrum figure of full-methylated cyclodextrinaniline nano supermolecule conducting polymer (PMPANI) in water and in the NaOH aqueous solution.
Fig. 3: full-methylated cyclodextrinaniline nano supermolecule conducting polymer (PMPANI) and the ultraviolet-visible-near-infrared spectrum figure of polyaniline (PANI) in the aqueous solution.
Fig. 4: full-methylated cyclodextrinaniline nano supermolecule conducting polymer (PMPANI)
1H NMR (D
2O) spectrogram.
Fig. 5: full-methylated cyclodextrinaniline nano supermolecule conducting polymer (PMPANI), polyaniline (PANI) and permethylated beta-cyclodextrin (PMCD)
1H NMR (D
2O) contrast of spectrogram.
Fig. 6: the IR spectrogram of full-methylated cyclodextrinaniline nano supermolecule conducting polymer (PMPANI), polyaniline (PANI) and permethylated beta-cyclodextrin/polyaniline physical mixture (PANI mix PMCD).
Fig. 7: the image of full-methylated cyclodextrinaniline nano supermolecule conducting polymer (PMPANI) under atomic force microscope (AFM).(substrate: mica)
Fig. 8: the image of full-methylated cyclodextrinaniline nano supermolecule conducting polymer (PMPANI) under transmission electron microscope (TEM).
Fig. 9: the AC resistivity data figure of full-methylated cyclodextrinaniline nano supermolecule conducting polymer (PMPANI) under differing temps.
Figure 10: the AC resistivity data figure of polyaniline (PANI) under differing temps.
Figure 11: (a) full-methylated cyclodextrinaniline nano supermolecule conducting polymer (PMPANI) specific conductivity varies with temperature figure.(b) the polyaniline specific conductivity varies with temperature figure.
Figure 12: wait under amount of substance PMPANI sample and the same terms synthetic polyaniline sonic oscillation 10 minutes in water, leave standstill the situation after 1 hour.
Figure 13: wait under amount of substance PMPANI sample and the same terms synthetic polyaniline sonic oscillation 10 minutes in water, leave standstill the situation after 5 hours.
[embodiment]
The polymerization gained takes place by the inclusion compound of aniline and permethylated beta-cyclodextrin in full-methylated cyclodextrinaniline nano supermolecule conducting polymer provided by the invention in acidic aqueous solution, monomer structure is as follows:
Preparation method of the present invention specifically describes as follows:
At first, shown in being prepared as follows of permethylated beta-cyclodextrin aniline inclusion compound:
Aniline is added in the aqueous solution of permethylated beta-cyclodextrin, after mixed system at room temperature stirs 5 hours, will can obtain the micro-yellow powder of permethylated beta-cyclodextrin aniline inclusion compound behind the solvent evaporate to dryness.
Prepare full-methylated cyclodextrinaniline nano supermolecule conducting polymer then, as follows:
Among the preparation method of the present invention, aqueous solvent used in the described preparation process is distilled water.Described aniline is that reagent is pure, and permethylated beta-cyclodextrin is for obtaining by known technology is synthetic.Described acidic aqueous solution is a hydrochloric acid, a kind of in perchloric acid or the aqueous sulfuric acid.The productive rate of polymkeric substance was the highest when described acidic aqueous solution was the aqueous hydrochloric acid of concentration 1.0-2.2M.Described oxygenant is an Ammonium Persulfate 98.5, Sodium Persulfate, Potassium Persulphate, a kind of in dichromic acid amine or the potassium bichromate.Described permethylated beta-cyclodextrin aniline inclusion compound is 1 with the ratio of the amount of substance of oxygenant: the productive rate of polymkeric substance is the highest during 1.0-1.5.But described permethylated beta-cyclodextrin aniline inclusion compound and oxygenant mixed system usually after the stirring reaction time is 15-24 hour primitive reaction complete.
The present invention is described further below by example:
Embodiment 1
The preparation method of full-methylated cyclodextrinaniline inclusion compound
93mg aniline is dissolved in the 30mL water, this aqueous solution is added in the aqueous solution (50mL) of the permethylated beta-cyclodextrin of 1.43g, mixed system at room temperature stirred 5 hours, will can obtain the micro-yellow powder of permethylated beta-cyclodextrin aniline inclusion compound behind the solvent evaporate to dryness.
Embodiment 2
The preparation method of full-methylated cyclodextrinaniline nano supermolecule conducting polymer
Under the room temperature the permethylated beta-cyclodextrin aniline of 1.5g inclusion compound is dissolved in the 30mL 1M hydrochloric acid fully, (concentration of hydrochloric acid in the 1-1.2M scope all can) stirs adding 2mL ammonium persulphate (0.5mol/L) solution down.(in the experimentation amount of substance of inclusion compound and ammonium persulphate than in 1.0-1.5 all can) solution gradually becomes light blue by little Huang, has blackish green precipitation to separate out after 2 hours gradually, solution colour is deepened, and progressively becomes deep green.After 15 hours, reaction finishes.The blackish green precipitation of separating out in the system is collected, and with distilled water wash for several times, vacuum-drying obtains blackish green pulverulent solids (productive rate: 80%, calculate with aniline monomer).
This compound can variable color in acid and alkaline environment, and this process is a reversible.
Embodiment 3
The nuclear-magnetism of full-methylated cyclodextrinaniline nano supermolecule conducting polymer and infrared spectra experiment
Fig. 5 is full-methylated cyclodextrinaniline nano supermolecule conducting polymer, permethylated beta-cyclodextrin and polyaniline
1HNMR spectrogram, solvent for use are deuterium for water.Wherein polyaniline is synthetic according to known technology.Can see that because the inclusion effect of methylated cyclodextrin increases the proton quantity of eigenstate phenyl ring (5.25ppm) in the polyaniline, it goes out the peak position and has also moved 0.15ppm to low field simultaneously.In addition, the proton peak that belongs to permethylated beta-cyclodextrin in the full-methylated cyclodextrinaniline nano supermolecule conducting polymer all has in various degree the branch that splits with respect to the parent permethylated beta-cyclodextrin, and the proton peak on its 3,5 moves to low simultaneously.These variations are because the inclusion effect of permethylated beta-cyclodextrin causes.
Fig. 6 is the infrared spectra comparison diagram of full-methylated cyclodextrinaniline nano supermolecule conducting polymer, polyaniline and permethylated beta-cyclodextrin/polyaniline physical mixture, and used is the KBr pressed disc method.Can see that the IR of full-methylated cyclodextrinaniline nano supermolecule conducting polymer composes 2900 to 2800cm
-1Near have more by force and to absorb, should belong to the flexural vibration peak of methyl in the methylated cyclodextrin.And at 1500-1600cm
-1Near absorption peak then should belong to the charateristic avsorption band of phenyl ring on the polyaniline.From with the comparison of the infrared spectra of polyaniline and permethylated beta-cyclodextrin/polyaniline physical mixture we are not difficult to find, the IR spectrogram of full-methylated cyclodextrinaniline nano supermolecule conducting polymer is not the simple superposition that the IR of polyaniline and permethylated beta-cyclodextrin composes.These experimental results have also effectively illustrated the existence of inclusion effect between permethylated beta-cyclodextrin and the polyaniline macromolecular chain.
The pattern of full-methylated cyclodextrinaniline nano supermolecule conducting polymer characterizes
Fig. 7 is the image of full-methylated cyclodextrinaniline nano supermolecule conducting polymer sample under atomic force microscope (AFM).Can see, be different from polyaniline, full-methylated cyclodextrinaniline nano supermolecule conducting polymer presents orderly wire aggregation structure.The height that we can draw aggregate from height map is about 2nm, and this matches with the platyopia exocoel diameter (about 1.65nm) of methylated cyclodextrin basically.Fig. 8 is the transmission electron microscope picture of aggregate.Wherein scheme b, figure c is the partial enlarged drawing of figure a.The transmission electron microscope picture of aggregate (Fig. 8) shows that to seem random wire aggregate spherical or ellipsoid shape aggregate is formed by many little nano levels.Their staggered linking to each other, formed the wire aggregation structure of big scale.This should be a kind of by a kind of transitional form between coccoid structure and club shaped structure
*As seen, the introducing of permethylated beta-cyclodextrin can induce the polyaniline polymer to form relatively than the dispersive aggregate structure.
Embodiment 5
Fig. 9,10 is respectively the full-methylated cyclodextrinaniline nano supermolecule conducting polymer sample and by the synthetic polyaniline that obtains of known technology resulting experimental data figure in the experiment of AC resistivity measurement.Horizontal ordinate zou is respectively the real part and the imaginary part of resistivity.Table 1 is according to Fig. 9, and 10 usefulness fitting of a curve are calculated the average resistivity and the specific conductivity of sample under the resulting certain temperature.Figure 12 is the conductivity variations figure of following two samples of differing temps.From these data drawing lists as can be seen, the full-methylated cyclodextrinaniline nano supermolecule conducting polymer sample descends to some extent than the synthetic down polyaniline specific conductivity that obtains of the same terms, but along with the rising of temperature, its specific conductivity rises gradually and rises very significantly between 80 ℃ to 100 ℃.This character obviously is different from the polyaniline specific conductivity and raises and downward trend with temperature.Simultaneously, the full-methylated cyclodextrinaniline nano supermolecule conducting polymer sample changes less and polyaniline descends obviously in this temperature range internal conductance rate 25 ℃ to 80 ℃ these wide temperature range internal conductance rates.
Table 1
| PMPANI | PANI | ||||
| T/℃ | ρ/Ω·m | σ/S·m -1 | T/℃ | ρ/Ω·m | σ/S·m -1 |
| 25 40 60 80 100 | 6.53× 10 3 3.74× 10 3 5.04× 10 3 2.49× 10 3 1.61× 10 2 | 1.53×10 -4 2.67× 10 -4 1.98× 10 -4 4.02× 10 -4 6.20× 10 -3 | 30 40 60 80 100 | 0.1 18 260 340 88 | 10.0 5.56× 10 -2 3.86× 10 -3 2.90× 10 -3 1.13× 10 -2 |
Deng the full-methylated cyclodextrinaniline nano supermolecule conducting polymer sample (PMPANI) of amount of substance with by known technology synthetic polyaniline (PANI) sonic oscillation after 10 minutes in 10mL distilled water, after leaving standstill 1 hour (Figure 13) and leaving standstill 5 hours (Figure 14), find that the PMAPNI sample can well be dispersed in aqueous phase.This explanation the water-soluble of full-methylated cyclodextrinaniline nano supermolecule conducting polymer will be significantly better than polyaniline.
Claims (10)
1. a full-methylated cyclodextrinaniline nano supermolecule conducting polymer is characterized in that the inclusion compound polymerization in acidic aqueous solution that is made of permethylated beta-cyclodextrin and aniline obtains, and its general structure is:
2. according to the described full-methylated cyclodextrinaniline nano supermolecule conducting polymer of claim 1, it is characterized in that: described polymkeric substance is under the condition of pure water at dispersion agent, its pattern yardstick is a nano level, aggregate by a plurality of little spherical or similar wire that the ellipticity object is formed, under 25 ℃-100 ℃, its average conductivity is 1.53 * 10
-4-1.53 * 10
-4Sm
-1
3. the preparation method of the described full-methylated cyclodextrinaniline nano supermolecule conducting polymer of claim 1 is characterized in that: the inclusion compound by described permethylated beta-cyclodextrin and aniline, in acidic aqueous solution, obtain, and its synthesis step comprises:
(1) aniline is soluble in water fully, this aqueous solution is added in the aqueous solution of permethylated beta-cyclodextrin, aniline is 1 with the ratio of the amount of substance of permethylated beta-cyclodextrin: 0.5-2.0;
(2) mixed system at room temperature stirred 5-10 hour, will can obtain the micro-yellow powder of permethylated beta-cyclodextrin aniline inclusion compound behind the solvent evaporate to dryness;
(3) under the room temperature micro-yellow powder of permethylated beta-cyclodextrin aniline inclusion compound is dissolved in the acidic aqueous solution of 0.5-3.0M fully, stirs and add aqueous oxidizing agent solution down; Permethylated beta-cyclodextrin aniline inclusion compound is 1 with the ratio of the amount of substance of oxygenant: 0.25-2.0;
(4) mixed system at room temperature stirred 15-24 hour, then the blackish green precipitation of separating out in the system was collected, and with distilled water wash for several times, vacuum-drying obtains blackish green pulverulent solids polymkeric substance.
4. according to the described preparation method of claim 3, it is characterized in that aqueous solvent used in the described preparation process is distilled water.
5. according to the described preparation method of claim 3, it is characterized in that described acidic aqueous solution is a hydrochloric acid, a kind of in perchloric acid or the aqueous sulfuric acid.
6. according to claim 3 or 6 described preparation methods, it is characterized in that described acidic aqueous solution is the aqueous hydrochloric acid of concentration 1.0-2.2M.
7. according to the described preparation method of claim 3, it is characterized in that described oxygenant is an Ammonium Persulfate 98.5, Sodium Persulfate, Potassium Persulphate, a kind of in dichromic acid amine or the potassium bichromate.
8. according to the described preparation method of claim 3, it is characterized in that the described permethylated beta-cyclodextrin aniline inclusion compound and the ratio of the amount of substance of oxygenant are 1: 1.0-1.5.
9. according to the described preparation method of claim 3, it is characterized in that described permethylated beta-cyclodextrin aniline inclusion compound and oxygenant mixed system are 15-24 hour in the stirring reaction time usually.
10. the full-methylated cyclodextrinaniline nano supermolecule conducting polymer of claim 1, in nano-supermolecule material technology field as application with nanoscale molecular lead of insulation layer.
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| CN101434664B (en) * | 2008-11-26 | 2010-11-24 | 南开大学 | Perylene-cyclodextrin nano supermolecule assembly, as well as preparation and application thereof |
| CN101613421B (en) * | 2009-05-08 | 2011-12-14 | 南开大学 | Anthraquinone-modified beta-cyclodextrin pseudo-polyrotaxane DNA non-covalent cross linking reagent |
| CN103409840A (en) * | 2013-07-15 | 2013-11-27 | 东华大学 | Method for preparing polyaniline nanofiber by using cyclodextrin as template |
| CN103467740A (en) * | 2013-09-09 | 2013-12-25 | 东华大学 | Method of preparing polyaniline nanometer tube with controllable pore diameter by taking beta-cyclodextrin as template |
| CN105255176A (en) * | 2015-10-10 | 2016-01-20 | 扬州大学 | Preparation method for carbon material-conducting polymer with controllable appearance |
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| CN1296411C (en) * | 2005-04-11 | 2007-01-24 | 重庆大学 | Method for preparing nano polyaniline |
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| CN101434664B (en) * | 2008-11-26 | 2010-11-24 | 南开大学 | Perylene-cyclodextrin nano supermolecule assembly, as well as preparation and application thereof |
| CN101613421B (en) * | 2009-05-08 | 2011-12-14 | 南开大学 | Anthraquinone-modified beta-cyclodextrin pseudo-polyrotaxane DNA non-covalent cross linking reagent |
| CN103409840A (en) * | 2013-07-15 | 2013-11-27 | 东华大学 | Method for preparing polyaniline nanofiber by using cyclodextrin as template |
| CN103409840B (en) * | 2013-07-15 | 2016-08-10 | 东华大学 | A kind of method preparing polyaniline nano fiber for template with cyclodextrin |
| CN103467740A (en) * | 2013-09-09 | 2013-12-25 | 东华大学 | Method of preparing polyaniline nanometer tube with controllable pore diameter by taking beta-cyclodextrin as template |
| CN103467740B (en) * | 2013-09-09 | 2015-12-23 | 东华大学 | Take beta-cyclodextrin as the method for the controlled polyaniline nanotube in Template preparation aperture |
| CN105255176A (en) * | 2015-10-10 | 2016-01-20 | 扬州大学 | Preparation method for carbon material-conducting polymer with controllable appearance |
| CN117683154A (en) * | 2024-01-31 | 2024-03-12 | 淄博千汇生物科技有限公司 | Preparation method of low-substitution degree methyl-beta-cyclodextrin |
| CN117683154B (en) * | 2024-01-31 | 2024-04-05 | 淄博千汇生物科技有限公司 | Preparation method of low-substitution degree methyl-beta-cyclodextrin |
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