CN108389677A - A kind of preparation method of novel water-based magnetic liquid - Google Patents
A kind of preparation method of novel water-based magnetic liquid Download PDFInfo
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- CN108389677A CN108389677A CN201810393827.1A CN201810393827A CN108389677A CN 108389677 A CN108389677 A CN 108389677A CN 201810393827 A CN201810393827 A CN 201810393827A CN 108389677 A CN108389677 A CN 108389677A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
- H01F1/445—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids the magnetic component being a compound, e.g. Fe3O4
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
- A61K31/716—Glucans
- A61K31/722—Chitin, chitosan
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
Abstract
The invention discloses a kind of preparation method of water-base magnetic liquid, which includes the following steps：1）, prepare Fe2+And Fe3+Molysite precursor solution, the excessive aqueous slkali dissolved with guanidine radicals chitosan is added into molysite precursor solution, under the conditions of nitrogen protection, reacts a period of time in certain temperature, nano cellulose crystal is added and stirs evenly and obtains magnetic liquid；2）, magnetic liquid purifying and single layer cladding handle：By 1）Obtained magnetic liquid is centrifuged successively, and after removing precipitation, ultrafiltration is carried out again after solution is carried out ultrasound.Characteristic of the preparation method of the water-base magnetic liquid of the present invention according to chitosan, the ultrasound for increasing specified conditions in purification process carry out single layer cladding processing, enhance the magnetism of water-base magnetic liquid.
Description
Technical field
The present invention relates to technical field of nano material, and in particular to a kind of preparation method of novel water-based magnetic liquid.
Background technology
Magnetic liquid is a kind of Nano-function thin films, is the grain size 10nm or so coated by surfactant
Magnetic-particle be dispersed in base load liquid, formed a kind of nanoscale, the mixing of solid-liquid two-phase stable homogeneous soliquid,
Layering and precipitating does not occur under impressed field.Magnetic liquid be a kind of mobility having both liquid with solid magnetic material to magnetic field
Therefore a kind of new function material of response characteristic is widely used in the multiple fields such as chemical industry, biology and clinical medicine.
Magnetic-particle can be divided into according to classification：Metal class has Fe, Co, Ni, Fe-Co, Fe-Ni alloy/C etc.；Nitrided iron class,
There are FeN, Fe3N、Fe4N、Fe16N2（Or Fe8N) etc.；Metal oxide-type mainly has Fe3O4, γ-Fe2O3, MFe2O4 (M =
Co, Mn, Ni etc.）.Fe3O4Magnetic-particle can rapidly be magnetized outside plus under magnetic fields, magnetic after externally-applied magnetic field removes
It disappears immediately again, no coercivity and remanent magnetism show excellent superparamagnetism, thus with special physical and chemical performance and receive
Meter Xing Neng.
Base load liquid mainly has water or aqueous solution, hydrocarbon, organic silicone oil perfluorinated liquids etc. as magnetic-particle
Carrier fluid.Corresponding carrier fluid is selected according to magnetic liquid difference purposes, with the mostly oil base class such as damping on mechanical seal, loud speaker
Magnetic liquid, and the magnetic liquid being applied to pharmaceutically is usually then using water as carrier fluid.
Using derivative-carboxymethyl chitosan of chitosan as synthesis of surfactant in patent CN 1702782A
Fe3O4Magnetic-particle water-base magnetic liquid, the magnetic liquid have biocompatibility, are suitable for medical domain；Its preparation used
Method is that surfactant is added while synthesizing magnetic particle to make synthesis and modified synchronous progress, in charging, carboxymethyl shell
Glycan is relative to Fe3O4Excessive, since synthesis and modification are carried out at the same time, reaction sequence and the extent of reaction are uncontrollable, will
There are Fe3O4The surfactant of magnetic-particle outer cladding is multilayer, and generates later Fe3O4Magnetic-particle cannot be by
The case where coating completely, and if carboxymethyl chitosan is added excessively, it will seriously lead to Fe3O4Magnetic-particle multilayer coating structure.And
Purification process in the patent is merely able to remove the Fe not coated completely3O4Magnetic-particle and uncoated carboxymethyl chitosan,
The Fe of multilayer coating structure can not be removed3O4The carboxymethyl chitosan of magnetic-particle excess surface becomes the Fe of single layer cladding3O4
Magnetic-particle, therefore influence whether the magnetism of final magnetic liquid obtained, to influence to apply.
Chitosan makes it due to having the characteristics that biodegradability, biocompatibility, biological non-toxicity and antibacterial activity
As one of the research hotspot of the exploitation of natural antibacterial agent in recent years.But due in chitosan molecule and intermolecular in the presence of a large amount of
Hydrogen bond, crystallinity is high, is insoluble in water, can only be dissolved in certain dilute acid solns, cause chitosan compared with traditional antiseptic
Antibacterial activity is low, to significantly limit promotion and application of the chitosan as antiseptic.In order to improve the water-soluble of chitosan
Property, people take a variety of methods.For example, the deacetylation of control chitosan is prepared into respectively between 50-60%, by chitosan
Kind inorganic acid or acylate carry out chemical modification to chitosan, can obtain water soluble chitosan or soluble derivative.
Although these methods have well solved chitosan water solubility problems, but anti-microbial property is not significantly improved.Chitosan molecule
It is upper to contain reactive hydroxyl and amino, it can be carried out as being acylated, carboxyl by controlling the reaction condition with hydroxyl or amino
Change, etherificate, NH2The reactions such as alkylation, esterification, hydrolysis introduce other groups and serial water-solubility chitosan derivative are made, to
Change its physical and chemical performance, assigns the more specific functions of chitosan and further widen shell to adapt to the needs of more areas
The scope of application of glycan.
Guanidine radicals is the strongest bioactivity organic base of electropositive that current nature is found, can under physiological pH medium
Protonation can form positively charged group under neutral, acid and alkaline condition.Guanidine compound is widely present in natural production
In object, dissolubility is strong, there is very strong alkalinity and electropositive.Guanidino group has anti-inflammatory, is depressured reducing blood lipid, is antiviral, is anti-swollen
The bioactivity such as tumor, while there is strong basicity, stiff stability, preferable bioactivity, and it is easily formed hydrogen chain, to very
Good anti-microbial property, is widely used in the fields such as medicine, agricultural, building, clothes, chemical industry.Therefore, guanidine radicals chitosan obtains
Extensive concern, guanidine radicals can be by electrostatic or hydrogen bond action in receptor and ligand, thus can play good drug effect, guanidine radicals
Compound, which is used as drug, mainly three kinds of drug for hypertension, hypoglycemic agent and antiviral agent.And the amino on chitosan has
Higher reactivity, therefore guanidinated modified its property similar with guanidine compound of imparting is carried out to chitosan by amino
Can, and then improve the bacteriostasis antibiosis performance of chitosan.
Nano cellulose crystal has distinctive colloid size, can form stable suspension in water for a long time, from
And its dispersibility in system and the compatibility with matrix are improved, there is low-density, high intensity and biodegradability.
Invention content
Based on the above technical problem, the present invention provides a kind of preparation method of novel water-based magnetic liquid.The water of the present invention
Based magnetic liquid prepares Fe using the precipitation method3O4Magnetic-particle, using guanidine radicals chitosan as surfactant to Fe3O4It is magnetic
Particle is modified, and makes it when applied to medical domain, with antibiotic property while with magnetic current bulk properties, is improved it and is answered
Use safety.Biodegradable nano cellulose crystal is added by the chitin modified Fe of guanidine radicals simultaneously3O4Magnetic-particle coats
Get up, enhances the stability of system.Also, characteristic of the preparation method of the present invention according to chitosan, increases in purification process
Add single layer cladding to handle, enhances the magnetism of water-base magnetic liquid.
In order to achieve the above object, the present invention uses following technical scheme：
Water-base magnetic liquid of the present invention, including Fe3O4Magnetic-particle, surfactant, nano cellulose crystal and work
For the water of base load liquid, the surfactant is guanidine radicals chitosan, has following molecular formula：
Wherein, x, y, n are natural number, 0 x≤10 ＜7, 102≦n≦107；
The preparation method of above-mentioned water-base magnetic liquid, includes the following steps：
1）, prepare Fe2+And Fe3+Molysite precursor solution, be added into molysite precursor solution it is excessive be dissolved with guanidine radicals shell
The aqueous slkali of glycan reacts a period of time in certain temperature, it is equal that nano cellulose crystal stirring is added under the conditions of nitrogen protection
It is even to obtain magnetic liquid；
2）, magnetic liquid purifying and single layer cladding handle：By 1）Obtained magnetic liquid is centrifuged successively, removes precipitation
Afterwards, ultrafiltration is carried out again after solution being carried out ultrasound；It is centrifuged off the Fe for failing to be wrapped by completely3O4Magnetic-particle, since surface does not have
Have by guanidine radicals Chitosan-coated, easily reunite, can settle down and remove after centrifugal treating；Ultrasound can make Fe3O4Magnetic
The excessive guanidine radicals chitosan of grain adsorption falls off the guanidine radicals chitosan for becoming free, and ultrafiltration removes the guanidine radicals chitosan that dissociates.By
Carboxyl, amino, alcoholic extract hydroxyl group and Fe are relied in guanidine radicals chitosan3O4Magnetic-particle surface action and be adsorbed on Fe3O4On magnetic-particle
Single layer cladding is formed, and extra guanidine radicals chitosan is to be adsorbed on Fe with intermolecular hydrogen bond action3O4The single layer packet of magnetic-particle
On coating, under certain ultrasound condition, the guanidine radicals chitosan of extra absorption can be made to be detached from, and the guanidine radicals chitosan of monolayer adsorption
Still stablize absorption.
Wherein, guanidine radicals chitosan prepares reference literature Zhai X., et.al., J. Appl. Polym. Sci.,
2011,121,3569. are prepared spare, dissolve the chitosan in olefin(e) acid aqueous solution, are reacted with cyanamide.Nanometer
Cellulose crystals select the KEXLAN CNC for the production for opening assist (CHEMKEY) company.
Preferably, the configuration of the molysite precursor solution is specially：It is 60%-70% that ferric trichloride, which is made into mass concentration,
Aqueous solution, ferrous chloride is configured to the aqueous solution of a concentration of 15%-30%, according to Fe2+：Fe3+= 1:The molar ratio of 1.5-2
Two kinds of solution are mixed and are made into molysite mixed solution.
Preferably, the aqueous slkali is 25% ammonium hydroxide.
Preferably, by guanidine radicals chitosan and 25% ammonium hydroxide with mass ratio 1:5-30 wiring solution-formings, heating keep guanidine radicals chitosan complete
Fully dissolved.It is highly preferred that the mass ratio of guanidine radicals chitosan and 25% ammonium hydroxide is 1:5-20.
Preferably, when excessive aqueous slkali dissolved with guanidine radicals chitosan being added into molysite precursor solution, guanidine radicals shell
The molar ratio of glycan and Fe elements is 1-6:1；It is highly preferred that the molar ratio of guanidine radicals chitosan and Fe elements is 1:1 or 2:1.
Preferably, the quality such as the addition of nano cellulose crystal and guanidine radicals chitosan.
Preferably, 1）Described in certain temperature be r.t.-100 DEG C, be for a period of time 0.5-2 h.
Preferably, the ultrasound condition is：Frequency is 20-50 kHz, and power is 120-300 W；It is highly preferred that frequency is
20-30 kHz, power are 120-200 W.
Beneficial effects of the present invention
Characteristic of the preparation method of the water-base magnetic liquid of the present invention according to chitosan, increases specified conditions in purification process
Ultrasound carries out single layer cladding processing, enhances the magnetism of water-base magnetic liquid.
Specific implementation mode
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment is served only for pair
The present invention is further described, and should not be understood as limiting the scope of the invention, and the person skilled in the art in the field can
To make some nonessential modifications and adaptations according to the content invented above.In the absence of conflict, the reality in the present invention
The feature applied in example and embodiment can be combined with each other.
Embodiment 1
By FeC13It is made into the aqueous solution that mass concentration is 60%, by FeCl2It is configured to a concentration of 15% aqueous solution, according to Fe2+：
Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 1.5 molar ratio.By guanidine radicals chitosan and 25% ammonium hydroxide with matter
Measure ratio 1:5 wiring solution-formings, heating make guanidine radicals chitosan be completely dissolved.It is added into molysite precursor solution excessive dissolved with guanidine
When the aqueous slkali of base enclosure glycan, it is 1 to make the molar ratio of guanidine radicals chitosan and Fe elements:1；It is stirred to react 0.5 at ambient temperature
H is added and is stirred evenly with the nano cellulose crystal of the quality such as guanidine radicals chitosan.Removing precipitation is centrifuged, obtains stabilization
Magnetic liquid, then carry out ultrafiltration, frequency is 20 kHz, and power is 120 W, removes in magnetic liquid and deposits using ultrafiltration method
Free state guanidine radicals chitosan, finally stablize magnetic liquid saturation magnetization be respectively 0.45 em μ/g.
Embodiment 2
By FeC13It is made into the aqueous solution that mass concentration is 65%, by FeCl2It is configured to a concentration of 20% aqueous solution, according to Fe2+：
Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 1.7 molar ratio.By guanidine radicals chitosan and 25% ammonium hydroxide with matter
Measure ratio 1:10 wiring solution-formings, heating make guanidine radicals chitosan be completely dissolved.Excessive be dissolved with is added into molysite precursor solution
When the aqueous slkali of guanidine radicals chitosan, it is 3 to make the molar ratio of guanidine radicals chitosan and Fe elements:1；It is stirred to react 1 under the conditions of 50 DEG C
H is added and is stirred evenly with the nano cellulose crystal of the quality such as guanidine radicals chitosan.Removing precipitation is centrifuged, obtains stabilization
Magnetic liquid, then carry out ultrafiltration, frequency is 25 kHz, and power is 150 W, removes in magnetic liquid and deposits using ultrafiltration method
Free state guanidine radicals chitosan, finally stablize magnetic liquid saturation magnetization be respectively 0.51 em μ/g.
Embodiment 3
By FeC13It is made into the aqueous solution that mass concentration is 70%, by FeCl2It is configured to a concentration of 30% aqueous solution, according to Fe2+：
Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 2 molar ratio.By guanidine radicals chitosan and 25% ammonium hydroxide with quality
Than 1:20 wiring solution-formings, heating make guanidine radicals chitosan be completely dissolved.It is added into molysite precursor solution excessive dissolved with guanidine
When the aqueous slkali of base enclosure glycan, it is 6 to make the molar ratio of guanidine radicals chitosan and Fe elements:1；It is stirred to react 2 under the conditions of 100 DEG C
H is added and is stirred evenly with the nano cellulose crystal of the quality such as guanidine radicals chitosan.Removing precipitation is centrifuged, obtains stabilization
Magnetic liquid, then carry out ultrafiltration, frequency is 30 kHz, and power is 200 W, removes in magnetic liquid and deposits using ultrafiltration method
Free state guanidine radicals chitosan, finally stablize magnetic liquid saturation magnetization be respectively 0.53 em μ/g.
Embodiment 4
By FeC13It is made into the aqueous solution that mass concentration is 65%, by FeCl2It is configured to a concentration of 15% aqueous solution, according to Fe2+：
Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 2 molar ratio.By guanidine radicals chitosan and 25% ammonium hydroxide with quality
Than 1:30 wiring solution-formings, heating make guanidine radicals chitosan be completely dissolved.It is added into molysite precursor solution excessive dissolved with guanidine
When the aqueous slkali of base enclosure glycan, it is 2 to make the molar ratio of guanidine radicals chitosan and Fe elements:1；It is stirred to react 0.5 at ambient temperature
H is added and is stirred evenly with the nano cellulose crystal of the quality such as guanidine radicals chitosan.Removing precipitation is centrifuged, obtains stabilization
Magnetic liquid, then carry out ultrafiltration, frequency is 50 kHz, and power is 300 W, precipitates, illustrates that ultrasonic power is somewhat high,
The guanidine radicals chitosan for single layer cladding occur falls off, and reunites under ultrasound condition, to precipitate.It is done using ultrafiltration after removing precipitation
Method removes free state guanidine radicals chitosan present in magnetic liquid, and the saturation magnetization for finally stablizing magnetic liquid is respectively
0.48 emμ/g。
Comparative example 1
By FeC13It is made into the aqueous solution that mass concentration is 65%, by FeCl2It is configured to a concentration of 15% aqueous solution, according to Fe2+：
Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 2 molar ratio.By carbonyl methyl chitosan and 25% ammonium hydroxide with matter
Measure ratio 1:30 wiring solution-formings, heating make carbonyl methyl chitosan be completely dissolved.Excessive dissolving is added into molysite precursor solution
When having the aqueous slkali of carbonyl methyl chitosan, it is 2 to make the molar ratio of carbonyl methyl chitosan and Fe elements:1；It stirs at ambient temperature
0.5 h is reacted, is added and is stirred evenly with the nano cellulose crystal of the quality such as guanidine radicals chitosan.It is heavy that removing is centrifuged
It forms sediment, obtains stable magnetic liquid, further use and do not inhaled by magnetic-particle present in ultrafiltration method removal magnetic liquid
Attached free state carbonyl methyl chitosan, the saturation magnetization for finally stablizing magnetic liquid is respectively 0.32 em μ/g.
Embodiment 1-4 carries out single layer cladding processing in purification process using ultrasound, and comparative example 1 is in purification process
Centrifugation and ultrafiltration are directly carried out, without the processing of single layer cladding, can be seen that from saturation magnetization, processing gained is coated by single layer
Water-base magnetic liquid saturation magnetization be above do not carry out single layer cladding processing water-base magnetic liquid.Also, super
Acoustic frequency reaches 50 kHz, when power is 300 W, occurs the guanidine radicals chitosan of single layer cladding since ultrasound intensity is excessively high and takes off
Fall sedimentation of reuniting.
Claims (10)
1. a kind of preparation method of water-base magnetic liquid, which is characterized in that include the following steps：
1) Fe, is prepared2+And Fe3+Molysite precursor solution, be added into molysite precursor solution it is excessive be dissolved with guanidine radicals shell
The aqueous slkali of glycan reacts a period of time in certain temperature, it is equal that nano cellulose crystal stirring is added under the conditions of nitrogen protection
It is even to obtain magnetic liquid；
2), the purifying of magnetic liquid and single layer cladding are handled：1) magnetic liquid obtained is centrifuged successively, removes precipitation
Afterwards, ultrafiltration is carried out again after solution being carried out ultrasound；
The water-base magnetic liquid, including Fe3O4Magnetic-particle, surfactant, nano cellulose crystal and as base load liquid
Water, the surfactant are guanidine radicals chitosan, have following molecular formula：
Wherein, x, y, n are natural number, 0 x≤10 ＜7, 102≦n≦107；
A diameter of 5~75nm of the nano cellulose crystal, length are 50~500nm.
2. preparation method according to claim 1, which is characterized in that the configuration of the molysite precursor solution is specially：
Ferric trichloride is made into the aqueous solution that mass concentration is 60%-70%, ferrous chloride is configured to the water-soluble of a concentration of 15%-30%
Liquid, according to Fe2+：Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by the molar ratio of 1.5-2.
3. preparation method according to claim 1, which is characterized in that the aqueous slkali is 25% ammonium hydroxide.
4. preparation method according to claim 3, which is characterized in that by carboxymethyl chitosan and 25% ammonium hydroxide with mass ratio
1:5-30 wiring solution-formings, heating make carboxymethyl chitosan be completely dissolved.
5. preparation method according to claim 3, which is characterized in that the mass ratio of carboxymethyl chitosan and 25% ammonium hydroxide is
1:5-20。
6. preparation method according to claim 1, which is characterized in that excessive dissolving is added into molysite precursor solution
When having the aqueous slkali of carboxymethyl chitosan, the molar ratio of carboxymethyl chitosan and Fe elements is 1-6:1.
7. preparation method according to claim 1, which is characterized in that excessive dissolving is added into molysite precursor solution
When having the aqueous slkali of carboxymethyl chitosan, the molar ratio of carboxymethyl chitosan and Fe elements is 1:1 or 2:1.
8. preparation method according to claim 1, which is characterized in that the addition of nano cellulose crystal is poly- with guanidine radicals shell
The quality such as sugar.
9. preparation method according to claim 1, which is characterized in that 1）Described in certain temperature be r.t.-100 DEG C, one
The section time is 0.5-2 h.
10. preparation method according to claim 1, which is characterized in that the ultrasound condition is：Frequency is 20-50 kHz,
Power is 120-300 W；It is highly preferred that frequency is 20-30 kHz, power is 120-200 W.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103525405A (en) * | 2013-10-21 | 2014-01-22 | 北京理工大学 | Magnetic fluorescent difunctional nano material based on natural polymer and preparation method thereof |
| CN107266610A (en) * | 2017-07-27 | 2017-10-20 | 山东百玛海洋生物科技有限公司 | The application of guanidinated chitosan derivative and nanoparticle |
| CN107610874A (en) * | 2017-10-18 | 2018-01-19 | 方利俊 | A kind of water-base magnetic liquid and preparation method thereof |
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2018
- 2018-04-27 CN CN201810393827.1A patent/CN108389677A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103525405A (en) * | 2013-10-21 | 2014-01-22 | 北京理工大学 | Magnetic fluorescent difunctional nano material based on natural polymer and preparation method thereof |
| CN107266610A (en) * | 2017-07-27 | 2017-10-20 | 山东百玛海洋生物科技有限公司 | The application of guanidinated chitosan derivative and nanoparticle |
| CN107610874A (en) * | 2017-10-18 | 2018-01-19 | 方利俊 | A kind of water-base magnetic liquid and preparation method thereof |
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