CN110387051A - A kind of preparation method of injectable type medical grade calcium alginate powder - Google Patents
A kind of preparation method of injectable type medical grade calcium alginate powder Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/06—Flowable or injectable implant compositions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/20—Materials or treatment for tissue regeneration for reconstruction of the heart, e.g. heart valves
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
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Abstract
The present invention discloses a kind of preparation method of injectable type medical grade calcium alginate powder, comprising the following steps: (1) preparation of sodium alginate soln: the preparation of (2) calcium ion component: the preparation of (3) calcium alginate gel: (4) calcium alginate gel cleaning: (5) calcium alginate powder preparation.The preparation method is simple, efficient, and liquid solvent used in whole process only has water for injection, and aqueous solvent is undoubtedly " green " solvent the most, and it is low in cost, without hazard residue, simple production process it is easy to operate, it can be achieved that calcium alginate field of tissue engineering technology clinical application.
Description
Technical field
The present invention relates to a kind of alginic acid alkali biomaterial for medical purpose, more particularly to a kind of injectable type medical grade seaweed
The preparation method of sour calcium powder, the medical grade calcium alginate powder are used to prepare cardiac muscle filling hydrogel.
Background technique
Alginate is based on the polysaccharide extracted in natural brown alga, and strand is ancient by beta-D-mannuronic acid (M) and α-L-
Sieve uronic acid (G) random block is copolymerized.Alginic acid alkali biomaterial has good biocompatibility, therefore is organizing
The bio-medical fields such as repair materials, biochemical drug control release carrier, cellular immunity isolation, cell transport and release are increasingly
It is valued by the people.And calcium alginate is a kind of alginate not soluble in water, has good edible safety, it is American-European,
Japan and other countries have been put into food additives, can be used as gelling thickener, calcium supplement etc..
Alginate biomaterial has the clinical application history of many years, has good clinical safety and validity,
Alginate biomaterial degradation rate in human body is low, has biologically inert and biomimetic features, can be good at maintaining cell
And tissue phenotype.According to investigation, in recent years nearly more than ten of II class alginate dressing of China each province and city CFDA approved, dentistry print
The products such as mould, medicament slow release and blood vessel embolism also obtain rapid progress.More it is worth noting that, alginate biomaterial is one
Good potentiality and application prospect are shown in terms of the Therapy study of a little clinical problems urgently to be solved, and relevant report is at home and abroad
It is reported in front academic periodical, and has related application, it is open such as Chinese patent CN1717265A, CN103480037B etc.
Myocardial injection alginate hydrogel treats heart failure, myocardial infarction.
Alginate hydrogel injection is implanted in left ventricular wall, plays the role of supporting ventricle wall as filler,
Ventricular structure can be improved and improve cardiac function, which can play good tissue scaffold function, increase ventricle wall thickness
Degree reduces ventricular chamber volume, reduces ventricle wall stress, increases ejection fraction, to prevent the deterioration of heart failure.
Studies have found that the purity of alginate has significant impact, current life to the biocompatibility of material
Production. art makes product contain the residual such as heavy metal, inorganic salts, albumen, polyphenol, endotoxin, this can all cause material to implant
Cause the adverse reactions such as allergy, fever, bleeding even shock, the presence of these impurity has seriously affected the biology peace of alginate
Full property and application.As announced in CN105504087B sodium alginate powder is dispersed in polar organic solvent be added can
Dissolubility calcium salt is come the method for preparing calcium alginate.5-90 μm of sodium alginate powder of specified particle diameter is needed in the prior art, is limited
The uses of raw material；And solvent is made using organic solvent, such as alcohols, acetone, acetonitrile, it is generally known that, organic solvent is chemistry
It is most common in technique, while being also the maximum contribution person of waste, many organic solvents are difficult acquisition environmental impact assessment and pass through, especially relate to
And organic solvent residual problem in medical instrument implantation class material, these organic solvents can all have damage effect to cell, unfavorable
In being chronically implanted, while organic solvent undoubtedly increases production cost and application risk.
World Calcium alginate powder is mainly technical grade, food-grade at present, as thickening in weaving, printing and dyeing, food
Agent, stabilizer, emulsifier and gelling agent, and there has been no industrialized products so far for the calcium alginate powder of used in tissue engineering, very
The research prepared to the calcium alginate about used in tissue engineering is all rarely reported.
Summary of the invention
In order to overcome commercialization in the prior art, calcium alginate impurity is more, purity is low, restricted to raw material particle size, organic
The shortcomings that dissolvent residual risk is high, is unable to satisfy organizational project application requirement, the purpose of the present invention is to provide a kind of injectables
The preparation method of type medical grade calcium alginate powder, whole preparation process only use water for injection as liquid solvent, not to original
Material particle size is limited, and be can be improved product quality, is suitable for field of tissue engineering technology, meets the phase of the biomaterial to implant
Close index request.
The purpose of the present invention is realized by following technical proposals:
A kind of preparation method of injectable type medical grade calcium alginate powder, comprising the following steps:
(1) preparation of sodium alginate soln: aseptically, water for injection is added in sterile pyrogen-free sodium alginate
In, it is uniformly dissolved, obtains sodium alginate soln, the concentration of the sodium alginate in the sodium alginate soln is 0.1-2wt%；
(2) calcium ion component: calcium ion component I is that aseptically, sterile pyrogen-free soluble calcium salt is added
It into water for injection, is uniformly dissolved, obtained ionic calcium soln, the concentration of the calcium salt in the ionic calcium soln is 50-
70wt%；Calcium ion component II is sterile pyrogen-free solubility calcium salt powder；
(3) prepared by calcium alginate gel: the calcium ion component I that step (2) are obtained or the calcium ion component
II is slowly added under continuous stirring in the sodium alginate soln of step (1) acquisition, and the time persistently stirred is 6-12
Hour, it reacts it sufficiently, obtains calcium alginate gel suspension；
(4) calcium alginate gel cleans: the calcium alginate gel suspension that step (3) are obtained is centrifuged, and makes seaweed
Sour calcium gel is separated from the water, then discards water phase, obtains calcium alginate gel, and it is solidifying to extract the calcium alginate with water for injection
Glue is then centrifuged for discarding water phase, repeatedly extracts the calcium alginate gel with water for injection and is then centrifuged for discarding water phase step
Suddenly, until the conductivity for discarding water phase is close with purifying water conductivity；
(5) prepared by calcium alginate powder: obtaining calcium alginate after the calcium alginate gel that step (4) obtains is dried
Blocks of solid aseptically grinds the calcium alginate blocks of solid, obtains alginic acid calcium powder after mesh screen classification
End.
The purpose of the present invention can also further realize by the following technical programs:
In one embodiment, soluble calcium salt described in step (2) is calcium chloride, calcium nitrate.
In one embodiment, use sterile pyrogen-free agate cream grinding device to the alginic acid in step (5)
Calcium blocks of solid is ground.
In one embodiment, mesh screen described in step (5) should be sterile apyrogeneity.
In one preferred embodiment, the preparation of calcium alginate powder described in step (5) is the condition in low temperature
It is lower to be ground.
In one preferred embodiment, the mesh screen is 50-1000 mesh.
It in one embodiment, further include that step (5) the calcium alginate powder is subjected to hot air sterilization or gamma
The step of being dispensed after sterilizing.
It in one embodiment, further include that step (5) the calcium alginate powder is configured to solution, packing, then
The step of carrying out gamma sterilization.
The present invention compared with the prior art, has the following advantages that and effect:
1, calcium alginate powder is prepared in the prior art to need, such as alcohols, acetone, acetonitrile, to exist using organic solvent
The risk of organic solvent residual, these organic solvents all can have damage effect to cell, influence the biology performance of material implantation；
Preparation method of the invention is simple, efficient, and liquid solvent used in whole process only has water for injection, and aqueous solvent is undoubtedly most
For " green " solvent, and low in cost, no hazard residue, simple production process is easy to operate, it can be achieved that calcium alginate is in group
Knit the clinical application of engineering field.
2, the partial size of raw material sodium alginate is required in the prior art, limits preparation process, increased preparation cost；
Sodium alginate need to only be dissolved in water for injection without Particle size requirements and be made into required solution by the sodium alginate raw material that the present invention uses
, greatly reduce the limitation to raw material.
3, medical grade calcium alginate powder-product prepared by method of the invention, product are stablized, and color is pure white, Neng Gouchong
Point dispersion in the solution, meets injectable needs, at the same can according to the calcium alginate powder of mesh screen aperture sub-sieve different-grain diameter,
Meet the application of regulation product different function.
Detailed description of the invention
Fig. 1 is calcium alginate powder.
Fig. 2 is alginic acid calcium powder solution.
Fig. 3 is one gained calcium alginate powder scanning electron microscopic picture of embodiment.
Fig. 4 is two gained calcium alginate powder scanning electron microscopic picture of embodiment.
Fig. 5 is three gained calcium alginate powder scanning electron microscopic picture of embodiment.
Specific embodiment
The present invention provides a kind of preparation methods of injectable type medical grade calcium alginate powder, include the following steps:
(1) preparation of sodium alginate soln: aseptically, water for injection is added in sterile pyrogen-free sodium alginate
In, it is uniformly dissolved, obtains sodium alginate soln, the concentration of the sodium alginate in the sodium alginate soln is 0.1-2wt%；
(2) calcium ion component: calcium ion component I is that aseptically, sterile pyrogen-free soluble calcium salt is added
It into water for injection, is uniformly dissolved, obtained ionic calcium soln, the concentration of the calcium salt in the ionic calcium soln is 50-
70wt%；Calcium ion component II is sterile pyrogen-free solubility calcium salt powder；
(3) prepared by calcium alginate gel: the calcium ion component I that step (2) are obtained or the calcium ion component
II is slowly added under continuous stirring in the sodium alginate soln of step (1) acquisition, reacts it sufficiently, obtains seaweed
Sour calcium gel suspension, the time persistently stirred are 6-12 hours；
(4) calcium alginate gel cleans: the calcium alginate gel suspension that step (3) are obtained is centrifuged, and makes seaweed
Sour calcium gel is separated from the water, then discards water phase, obtains calcium alginate gel, and it is solidifying to extract the calcium alginate with water for injection
Glue is then centrifuged for discarding water phase, repeatedly extracts the calcium alginate gel with water for injection and is then centrifuged for discarding water phase step
Suddenly, until the conductivity for discarding water phase is close with purifying water conductivity；
(5) prepared by calcium alginate powder: obtaining calcium alginate after the calcium alginate gel that step (4) obtains is dried
Blocks of solid aseptically carries out the calcium alginate blocks of solid using sterile pyrogen-free agate cream grinding device
Grinding, carries out grain size grading with the sterile apyrogeneity mesh screen of 50-1000 purpose, obtains calcium alginate powder.
Embodiment one:
1, the preparation of sodium alginate soln: aseptically, injection is added in sterile pyrogen-free sodium alginate 2g
In water in 98mL, mechanical stirring 8h sufficiently dissolves, and obtains sodium alginate soln, system concentration 2wt%；Seaweed used herein
Sour sodium is medical grade sodium alginate, can be completely dissolved in aqueous solution, not require the partial size of sodium alginate raw material,
Any organic solvent is not used simultaneously；
2, calcium ion component: choosing calcium chloride, and the amount of calcium chloride is 5 times of equivalents of sodium ion in sodium alginate, alginic acid
The repetitive unit molecular weight of sodium is that sodium ion is 10.101mmol in 198.0,2g sodium alginate, and calcium chloride should be
50.505mmol, the molecular weight of calcium chloride is 110.9, therefore calcium chloride should be 5.6g, and aseptically, calcium chloride is added to
It in water for injection, is uniformly dissolved, is configured to the aqueous solution of 50wt%；It is to make sea that calcium chloride, which is made into highly concentrated solution, herein
The yield that mosanom is converted into calcium alginate improves；
3, prepared by calcium alginate gel: in lasting whipping process, ionic calcium soln being slowly added to sodium alginate soln
In, and continue to stir 12h, it reacts it sufficiently and obtains calcium alginate gel；High concentration calcium ion solution is added drop-wise to sodium alginate
In solution, since ionic calcium soln concentration is big, so that beginning to react simultaneously shape when ionic calcium soln is contacted with sodium alginate soln
At gel precipitation, reaction yield is high, and sodium alginate is fully converted to calcium alginate, obtains broken calcium alginate gel and is suspended
Liquid；
4, calcium alginate gel cleans: calcium alginate gel suspension is centrifuged, keeps calcium alginate gel separated from the water,
Water phase is discarded, calcium alginate gel is obtained, extracts calcium alginate gel with water for injection, is then centrifuged for discarding water phase, repeats to use
Water for injection extracts the calcium alginate gel and is then centrifuged for discarding water phase step 20 time, until water phase conductivity and purifying water power
Conductance is close, and the conductivity of water phase is close to 6.8 μ S/cm；
5, prepared by calcium alginate powder: calcium alginate bulk is obtained after calcium alginate gel obtained above is dried
Solid aseptically grinds blocks of solid using sterile pyrogen-free agate cream grinding device, with the net of 200 mesh
Sieve carries out grain size grading, obtains calcium alginate powder, as shown in figure 3, being gained calcium alginate powder scanning electron microscopic picture；
6, use is dispensed after above-mentioned calcium alginate powder being carried out hot air sterilization or gamma sterilization, as shown in Figure 1.
Embodiment two:
1, the preparation of sodium alginate soln: aseptically, injection is added in sterile pyrogen-free sodium alginate 1g
In water in 99mL, mechanical stirring 5h sufficiently dissolves, and obtains sodium alginate soln, system concentration 1wt%；
2, calcium ion component: choosing calcium nitrate, and the amount of calcium nitrate is 10 times of equivalents of sodium ion in sodium alginate, alginic acid
The repetitive unit molecular weight of sodium is that sodium ion is 5.051mmol in 198.0,1g sodium alginate, and calcium nitrate should be 50.51mmol,
The molecular weight of calcium nitrate is 164.1, therefore calcium nitrate should be 8.29g, aseptically, weigh nitric acid calcium powder；
3, prepared by calcium alginate gel: nitric acid calcium powder is slowly added to by sodium alginate soln in lasting whipping process
Wherein, and continue to stir 12h, react it sufficiently and obtain calcium alginate gel suspension；
4, calcium alginate gel cleans: calcium alginate gel suspension is centrifuged, keeps calcium alginate gel separated from the water,
Water phase is discarded, calcium alginate gel is obtained, extracts calcium alginate gel with water for injection, is then centrifuged for discarding water phase, repeats to soak
It mentions 20 times, until water phase conductivity is close with water conductivity is purified, the conductivity of water phase is close to 6.8 μ S/cm；
5, calcium alginate powder prepare: by calcium alginate gel obtained above, aseptically to blocks of solid into
The powder of row freeze grinding, grinding is dried, and obtains powdered calcium alginate, carries out partial size point with the mesh screen of 50 mesh
Grade, obtains calcium alginate powder, as shown in figure 4, being gained calcium alginate powder scanning electron microscopic picture.
6, use is dispensed after above-mentioned calcium alginate powder being carried out hot air sterilization or gamma sterilization.
Embodiment three
1, the preparation of sodium alginate soln: aseptically, injection is added in sterile pyrogen-free sodium alginate 0.1g
With in 99.9mL, mechanical stirring 10h sufficiently dissolves in water, sodium alginate soln, system concentration 0.1wt% are obtained；Make herein
Sodium alginate is medical grade sodium alginate, can be completely dissolved in aqueous solution, to the partial size of sodium alginate raw material
It does not require, while not using any organic solvent；
2, calcium ion component: choosing calcium chloride, and the amount of calcium chloride is 5 times of equivalents of sodium ion in sodium alginate, alginic acid
The repetitive unit molecular weight of sodium is that sodium ion is 0.505mmol in 198.0,0.1g sodium alginate, and calcium chloride should be
2.525mmol, the molecular weight of calcium chloride is 110.9, therefore calcium chloride should be 0.28g, and aseptically, calcium chloride is added to
It in water for injection, is uniformly dissolved, is configured to the aqueous solution of 70wt%；It is to make sea that calcium chloride, which is made into highly concentrated solution, herein
The yield that mosanom is converted into calcium alginate improves；
3, prepared by calcium alginate gel: in lasting whipping process, ionic calcium soln being slowly added to sodium alginate soln
In, and continue to stir 6h, it reacts it sufficiently and obtains calcium alginate gel；It is molten that high concentration calcium ion solution is added drop-wise to sodium alginate
In liquid, since ionic calcium soln concentration is big, so that beginning to react and formed when ionic calcium soln is contacted with sodium alginate soln
Gel precipitation, reaction yield is high, and sodium alginate is fully converted to calcium alginate, obtains broken calcium alginate gel suspension；
4, calcium alginate gel cleans: calcium alginate gel suspension is centrifuged, keeps calcium alginate gel separated from the water,
Water phase is discarded, calcium alginate gel is obtained, extracts calcium alginate gel with water for injection, is then centrifuged for discarding water phase, repeats to use
Water for injection extracts the calcium alginate gel and is then centrifuged for discarding water phase step 20 time, until water phase conductivity and purifying water power
Conductance is close, and the conductivity of water phase is close to 6.8 μ S/cm；
5, prepared by calcium alginate powder: calcium alginate bulk is obtained after calcium alginate gel obtained above is dried
Solid aseptically carries out cryogrinding to blocks of solid, is preferably ground with liquid nitrogen frozen, then with the mesh screen of 1000 mesh
Grain size grading is carried out, calcium alginate powder is obtained, as shown in figure 5, being gained calcium alginate powder scanning electron microscopic picture；
6, above-mentioned calcium alginate powder is configured to solution, packing, then carries out gamma sterilization use, as shown in Figure 2.
Using ultrapure sodium alginate as raw material, ultrapure sodium alginate need to be only completely dissolved the present invention by no partial size limitation
In aqueous solution, whole preparation process is not necessarily to any organic solvent, and the calcium alginate prepared is residual without any organic solvent
It stays.The calcium alginate of the method production is gel during the preparation process, and subsequent drying and grinding is needed to handle, and is obtained after grinding sub-sieve
The powder good dispersion degree arrived is easily dispersed after wiring solution-forming.
Finally it should be noted that the foregoing is merely preferred embodiment of the invention, it is not limited to this
Invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in this hair
Within bright protection scope.
Claims (7)
1. a kind of preparation method of injectable type medical grade calcium alginate powder, which comprises the following steps:
(1) preparation of sodium alginate soln: aseptically, sterile pyrogen-free sodium alginate being added in water for injection,
It is uniformly dissolved, obtains sodium alginate soln, the concentration of the sodium alginate in the sodium alginate soln is 0.1-2wt%；
(2) calcium ion component: calcium ion component I is aseptically, sterile pyrogen-free soluble calcium salt to be added to note
It penetrates in water, is uniformly dissolved, obtained ionic calcium soln, the concentration of the calcium salt in the ionic calcium soln is 50-70wt%；Calcium
Ion component II is sterile pyrogen-free solubility calcium salt powder；
(3) prepared by calcium alginate gel: the calcium ion component I or the calcium ion component II of step (2) acquisition are existed
It being slowly added into the sodium alginate soln of step (1) acquisition under lasting stirring, the time persistently stirred is 6-12 hours,
It reacts it sufficiently, obtains calcium alginate gel suspension；
(4) calcium alginate gel cleans: the calcium alginate gel suspension that step (3) are obtained is centrifuged, and makes calcium alginate
Gel is separated from the water, then discards water phase, obtains calcium alginate gel, extracts the calcium alginate gel with water for injection,
It is then centrifuged for discarding water phase, repeatedly extracts the calcium alginate gel with water for injection and be then centrifuged for discarding water phase step,
Until the conductivity for discarding water phase is close with purifying water conductivity；
(5) prepared by calcium alginate powder: calcium alginate bulk is obtained after the calcium alginate gel that step (4) obtains is dried
Solid aseptically grinds the calcium alginate blocks of solid, obtains calcium alginate powder after mesh screen classification.
2. the preparation method of injectable type medical grade calcium alginate powder according to claim 1, it is characterised in that: step
(5) the calcium alginate blocks of solid is ground using sterile pyrogen-free agate cream grinding device in.
3. the preparation method of injectable type medical grade calcium alginate powder according to claim 1, it is characterised in that: described
Mesh screen described in step (5) is sterile apyrogeneity.
4. the preparation method of injectable type medical grade calcium alginate powder according to claim 1, it is characterised in that: step
(5) preparation of calcium alginate powder described in is ground under conditions of low temperature.
5. the preparation method of injectable type medical grade calcium alginate powder according to claim 1, it is characterised in that: also wrap
The step of including to being dispensed after calcium alginate powder progress hot air sterilization or gamma sterilization.
6. the preparation method of injectable type medical grade calcium alginate powder according to claim 1, it is characterised in that: also wrap
The step of including and solution, packing be configured to the calcium alginate powder, then carrying out gamma sterilization.
7. the preparation method of injectable type medical grade calcium alginate powder according to claim 1, it is characterised in that: step
(2) soluble calcium salt described in is calcium chloride, calcium nitrate.
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Cited By (4)
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| CN110693725A (en) * | 2019-10-31 | 2020-01-17 | 厦门大学附属中山医院 | Calcium alginate gel tooth root canal filling material and preparation method thereof |
| CN110862561A (en) * | 2019-11-19 | 2020-03-06 | 青岛明月藻酸盐组织工程材料有限公司 | Preparation method of water-insoluble alginate for in vivo implantation |
| CN111418800A (en) * | 2020-05-15 | 2020-07-17 | 青岛明月海藻生物健康科技集团有限公司 | Instant quick-setting jelly powder, preparation method and preparation method of jelly |
| CN115216031A (en) * | 2022-07-28 | 2022-10-21 | 康迪菲（苏州）生物科技有限公司 | In-situ sodium alginate hydrogel disposable glove and preparation method thereof |
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| CN104804109A (en) * | 2014-01-25 | 2015-07-29 | 青岛海之林生物科技开发有限公司 | Preparation method and application of dissolving injectable calcium alginate base |
| CN105504087A (en) * | 2016-01-28 | 2016-04-20 | 杭州琅达医疗科技有限公司 | Medical grade calcium alginate preparing method |
| CN107973863A (en) * | 2017-11-30 | 2018-05-01 | 江苏中大生物科技集团有限公司 | A kind of sodium alginate preparation method based on powder morphology adsorbing separation |
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