CN101230150B - Method for preparing pure sodium alginate nano fiber membrane material - Google Patents
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Abstract
The invention belongs to the macromolecule material technology field, which relates to a preparation method of biodegradable and bio-absorbable macromolecule nanometer fiber non-woven fabric material, in particular to the preparation method of natural high polymer biological material, namely, sodium alginate electrostatic spinning solution, and the preparation method of pure sodium alginate nanometer fiber membrane material. The preparation method and the technical principle of the invention comprise the following steps: aiming at the characteristics of rigidity and stretching ability of the sodium alginate molecular chain in the aqueous solution, a solvent type strong polar modifying agent, namely, polyhydroxylated compound is induced in the aqueous solution of the sodium alginate, and through the strong polarity and the low surface tensile force, etc. of the compound, the physical property of the aqueous solution of the sodium alginate is effectively adjusted, thereby realizing thatthe transforming from the non-spinning of the aqueous solution of the sodium alginate to the spinning of the aqueous solution of the sodium alginate, and obtaining the even and smooth pure sodium alginate nanometer fiber membrane material.
Description
Technical field
The invention belongs to technical field of polymer materials, but the preparation method who relates to biodegradable and bio-absorbable high polymer nanometer fiber nonwoven cloth material, particularly a kind of natural polymer biomaterial---the preparation of sodium alginate electrostatic spinning stoste and the preparation method of pure sodium alginate nano fiber membrane material thereof.
Background technology
Sodium alginate (SA) is a kind of polyuronide of the line style of extracting from natural brown alga, passes through 1 by α-L-guluronic acid (G unit) and beta-D-mannuronic acid (M unit), connection of 4-glycosidic link and the random copolymers of being made up of different GGGMMM fragments.The concentration of G and M (G: the M ratio) determined characteristics such as structure that SA is different and biocompatibility.SA has the nature and characteristic of polyanion electrolyte, and its relative molecular weight is 10
6About, be a kind of degradable biological polymer.Because of its excellent biological compatibility, hypotoxicity and relative cheap price have broad application prospects at drug delivery system, field of tissue engineering technology and pharmacy field.From biological angle, nearly all tissue and organ all exist with nanofiber or nanostructure, as bone, and tooth, cartilage and skin etc.And traditional dry method and wet-spinning can only be produced diameter at several microns fibers to the hundreds of micron.Method of electrostatic spinning is a kind of simply and effectively complete processing for preparing polymer superfine fibre.But because electrostatic spinning technique using electric field power but not mechanical force is carried out the fiber manufacturing, so this technology has some special requirements to the character of solution, as the viscosity of solution, chain entanglement degree etc.The pure sodium alginate aqueous solution is (referring to Fig. 1) (Adv.Mater.2006,18,1463～1467 that can not carry out electrostatic spinning according to the literature; Polymer 2007,47, and 8026～8023; J.Appl.Polym.Sci.2007,106,1855～1859; J.Appl.Polym.Sci.2007,104,3245～3255.), but assisting down of other water-soluble synthetic macromolecule, then can realize the electrostatic spinning of sodium alginate aqueous solution, as publication number is in the Chinese patent " being nano fiber scaffold material of matrix and preparation method thereof with the sodium alginate " of CN101011597A, discloses the preparation method of this technology.Its technical scheme is to be matrix with the sodium alginate, under polyoxyethylene or polyvinyl alcohol and a spot of glycerol effect, can obtain the fibrous framework material of Fibre diameter at 50～500nm by electrostatic spinning.But the fiber of gained is the blend fiber of sodium alginate and polyoxyethylene and sodium alginate and polyvinyl alcohol like this, and how to realize that the electrostatic spinning of pure sodium alginate still belongs to blank at present.
Sodium alginate is a kind of water miscible natural polysaccharide, has the insoluble character of multiple organic solvent, and in the aqueous solution because the expansion of the rigidity of polymer backbone itself, chain that charged group causes or the interaction of polymer segment and water molecules etc. all make the molecular chain of sodium alginate manifest extensibility highly, lack enough molecular entanglements, thereby brought great obstruction for the electrostatic spinning of sodium alginate.Thereby all do not see the bibliographical information of relevant pure sodium alginate electrostatic spinning so far.
The present invention selects for use water or water and alcoholic acid mixture to make solvent, constructional feature at the sodium alginate molecular chain, by adding the SOLUTION PROPERTIES that a kind of solvent type properties-correcting agent is regulated sodium alginate, overcome the unfavorable factor on the sodium alginate self structure, can prepare even thickness even the controlled pure sodium alginate nano fiber of Fibre diameter continuously, fill up this technological gap.Sodium alginate nano fiber film with the electrostatic spinning technique preparation has excellent biological compatibility, biological degradability and bio-absorbable performance, can be used for hemostatic material, the wound coating material, tissue engineering bracket material, drug releasing membrane according, aspects such as artificial skin, artificial blood vessel, wound dressing, drug conveying, microbial film, beauty treatment material.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of preparation method of pure sodium alginate nano fiber membrane material is provided.
Another object of the present invention is to fill up the technological gap of realizing on the pure sodium alginate electrostatic spinning, a kind of pure sodium alginate electrostatic spinning solution nontoxic, with low cost is provided, with the electrostatic spinning of realization pure sodium alginate solution, and obtain corresponding pure sodium alginate nano fiber membrane material.
Preparation method of the present invention and know-why thereof are: at rigidity and the extensibility characteristics of sodium alginate molecular chain in the aqueous solution, we introduce a kind of solvent type strong polar properties-correcting agent-polyol in the aqueous solution of sodium alginate, effectively regulate the physical properties of sodium alginate aqueous solution by the strong polarity of this compound and low surface tension etc., thereby realize sodium alginate soln from can not spinning spinnable transformation, and obtain uniform and smooth pure sodium alginate nano fiber.
The preparation method of pure sodium alginate nano fiber membrane material of the present invention may further comprise the steps:
1) preparation of sodium alginate electrostatic spinning stoste: for fast sodium alginate being dissolved into solution, the raw material sodium alginate is dispersed in the properties-correcting agent, wherein the weightmeasurement ratio of sodium alginate and properties-correcting agent is 2g/ml%～4g/ml%, and then in above-mentioned mixing solutions, add solvent, wherein the volume ratio of solvent and properties-correcting agent is 0.5～1 (concentration of raw material sodium alginate is 1g/ml%～2.67g/ml%) in whole system, wherein solvent and properties-correcting agent all by volume calculate), after waiting to stir, the static bubble that separates out promptly obtains sodium alginate electrostatic spinning stoste.
Solvent in the technique scheme is selected from water or water and ethanol mixed solvent, and wherein water and alcoholic acid volume ratio are 2: 1～3: 1 in the mixed solvent; Described raw material sodium alginate is that 2% soltion viscosity is greater than 3500 centipoises at 25 ℃ of mass percent concentrations; Described properties-correcting agent is that (wherein: the volume ratio of glycerine and ethylene glycol is 50～100: 50～0) for the mixture of polyol glycerine or glycerine and ethylene glycol.
2) electrostatic spinning process: the sodium alginate electrospinning silk stock solution that step 1) is obtained is injected in the electrostatic spinning apparatus feeding device of (as shown in Figure 4), the feeding rate of adjusting sodium alginate electrospinning silk stock solution is 5～300 μ l/min, and preferred feeding rate is 10～150 μ l/min; Distance between the spinning nozzle of feeding device and the collector of ground connection is 5～25cm, is preferably 7～20cm; Envrionment temperature is 20～70 ℃, is preferably 20～40 ℃; The air velocity of environment is 0～8.5m
3/ hr is preferably 0.5～5m
3/ hr; Open high-voltage power supply, voltage is 1～60kV, is preferably 20～30kV, opens the feeding device pump that sodium alginate electrospinning silk stock solution is housed, injection stream is ejected on the collector, but obtains the pure sodium alginate nano fiber membrane material of biodegradable and bio-absorbable on collector.The mean diameter of pure sodium alginate nano fiber is 80nm～1 μ m.
Because the difficult volatility of properties-correcting agent in the solvent, therefore described when on collector, collecting fiber, need collector to be fully immersed in and contain CaCl
2In the precipitation bath of (linking agent of sodium alginate), in the fiber pattern that keeps the electrospinning sodium alginate, so that can more effective residual solvent and the properties-correcting agent (referring to accompanying drawing 4) removed.
The described collector that is fully immersed in the precipitation bath is wire netting or metal plate etc.; Described precipitation bath is that mass percent concentration is 5%～10% CaCl
2The aqueous solution and the mixed solution of dehydrated alcohol, wherein the volume percent of dehydrated alcohol in mixing solutions is 60～80%.
Step 2 of the present invention) but the pure sodium alginate nano fiber membrane material of obtain biodegradable and bio-absorbable can further soak 2～24 hours to remove residual solvent in dehydrated alcohol, and with dehydrated alcohol repeatedly the drip washing tunica fibrosa washed away fully until remaining spin solvent, with tunica fibrosa vacuum-drying after 0.5～50 hour in 20～60 ℃ of vacuum drying ovens, obtain the pure sodium alginate nano fiber membrane material (referring to Fig. 2 and 3) of the biology of biodegradable and absorption, place moisture eliminator to preserve.
The invention discloses a kind of preparation method who adopts electrostatic spinning process to prepare pure sodium alginate nano fiber membrane material.By in the pure sodium alginate aqueous solution that can not spin, adding properties-correcting agent, realized that sodium alginate is from spinning spinnable transformation, the pure sodium alginate nano fiber membrane material that obtains is made up of the alginates of 100% component, belongs to a kind of biopolymer micro/nano fibrous membrane material that can degrade fully and absorb.The present invention is directed to the characteristics of sodium alginate soln system after the modification, adopted the receiving device of band precipitation bath, finally prepared Fibre diameter at the pure sodium alginate fiber film material of tens nanometers to the hundreds of nanometer.Electrostatic spinning stoste of the present invention has high-performances such as nontoxic, with low cost.Prepared pure sodium alginate nano fiber membrane material can be used as medical tissue engineering scaffold material, drug releasing membrane according, artificial skin, wound dressing, drug conveying, microbial film (matrix of immobilized enzyme and catalyst system), wound coated material, hemostatic material, wound coating material and beauty treatment material etc.
Description of drawings
Fig. 1 is that the sodium alginate aqueous solution that does not add polyol adopts electrostatic spinning technique to collect the SEM pattern of the product that obtains.
Fig. 2 is the SEM pattern that the sodium alginate soln for preparing by the technical scheme that the embodiment of the invention 1 is provided adopts the product that electrostatic spinning technique collects.
Fig. 3 is the SEM pattern that the sodium alginate soln for preparing by the technical scheme that the embodiment of the invention 2 is provided adopts the product that electrostatic spinning technique collects.
Fig. 4 is the electrospinning receiving trap that adopts at the difficult volatility characteristics of solvent, properties-correcting agent.
Embodiment
The electrostatic spinning apparatus that adopts among the embodiment as shown in Figure 4; The raw material sodium alginate is at 25 ℃, and mass percent concentration is 2% the soltion viscosity sodium alginate (U.S. Sigma company) greater than 3500 centipoises.
Embodiment 1
The first step: with viscosity is that the sodium alginate of 3500 centipoises is a raw material, and properties-correcting agent is glycerine, at normal temperatures sodium alginate is dispersed in the glycerine, and wherein the weightmeasurement ratio of sodium alginate and glycerine is 4g/ml%.
Second step: add aqueous solvent in above-mentioned suspension, wherein the volume ratio of water and glycerine is 1, continues to stir, until the solution of being dissolved into homogeneous transparent.
The 3rd step: the above-mentioned solution of removing bubble that leaves standstill is injected in the electrostatic spinning container, spinning temperature is room temperature (25 ℃), the high-voltage power supply output voltage is 28KV, and feeding rate is 108 μ l/min, and the distance between collector (metal copper mesh) and the spinning nozzle is 12cm.The feeding device pump of sodium alginate electrospinning silk stock solution is equipped with in unlatching, and injection stream is ejected on the collector, the electrostatic spinning process stabilization, and (precipitation bath is that mass percent concentration is 10% CaCl all being immersed in collector in the precipitation bath
2The mixed solution of the aqueous solution and dehydrated alcohol, wherein the volume percent of dehydrated alcohol in mixing solutions is 80%) on receive tunica fibrosa.
The 4th step: collected tunica fibrosa is soaked 3 hours to remove the residuary water solvent in dehydrated alcohol, and with the continuous drip washing tunica fibrosa of dehydrated alcohol 3 times, at last with tunica fibrosa vacuum-drying after 12 hours in 50 ℃ of vacuum drying ovens, obtain a kind of fully biodegradable of forming by the alginate of 100% component and the micro/nano fibrous membrane material of bio-absorbable, can be used for organizational project and aspects such as drug delivery and beauty treatment material.Can be clear that (see figure 2) by sem photograph, the nanofiber diameter of preparation is about 150nm.
Embodiment 2
The first step: with viscosity is that the sodium alginate of 3500 centipoises is a raw material, and properties-correcting agent is glycerine, at normal temperatures sodium alginate is dispersed in the properties-correcting agent, and wherein the weightmeasurement ratio of sodium alginate and glycerine is 3g/ml%.
Second step: add aqueous solvent in above-mentioned suspension, wherein the volume ratio of water and glycerine is 0.5, continues to stir, until the solution of being dissolved into homogeneous transparent.
The 3rd step: the above-mentioned solution of removing bubble that leaves standstill is injected in the electrostatic spinning container, and spinning temperature is a room temperature, and the high-voltage power supply output voltage is 28KV, and feeding rate is 108 μ l/min, and collector (metal copper mesh) and the distance that goes out between the spinning nozzle are 12cm.The feeding device pump of sodium alginate electrospinning silk stock solution is equipped with in unlatching, and injection stream is ejected on the collector, the electrostatic spinning process stabilization, and (precipitation bath is that mass percent is 10% CaCl to the collector in being fully immersed in precipitation bath
2The mixed solution of the aqueous solution and dehydrated alcohol, wherein the volume percent of dehydrated alcohol in mixing solutions is 60%) on receive tunica fibrosa.
The 4th step: collected tunica fibrosa is soaked 3 hours to remove the residuary water solvent in dehydrated alcohol, and with the continuous drip washing tunica fibrosa of dehydrated alcohol 3 times, at last with tunica fibrosa vacuum-drying after 12 hours in 50 ℃ of vacuum drying ovens, obtain a kind of fully biodegradable of forming by the alginate of 100% component and the micro/nano fibrous membrane material of bio-absorbable, can be used for organizational project and aspects such as drug delivery and beauty treatment material.Can be clear that (see figure 3) by sem photograph, the nanofiber diameter of preparation is about 200nm.
Embodiment 3
The first step: with viscosity is that the sodium alginate of 5000 centipoises is a raw material, properties-correcting agent is the mixture (volume ratio of glycerine and ethylene glycol is 3: 1) of glycerine and ethylene glycol, at normal temperatures sodium alginate is dispersed in the properties-correcting agent, wherein the weightmeasurement ratio of sodium alginate and mixed modifier is 3.0g/ml%.
Second step: (water and ethanol volume ratio are 2: 1, and wherein solvent (being water and alcoholic acid cumulative volume) is 4: 3 with the volume ratio of properties-correcting agent, continue to stir, until the solution of being dissolved into homogeneous transparent to add aqueous solvent and alcoholic acid mixed solution in above-mentioned suspension.
The 3rd step: the above-mentioned solution of removing bubble that leaves standstill is injected in the electrostatic spinning container, and spinning temperature is a room temperature, and the high-voltage power supply output voltage is 28KV, and feeding rate is 120 μ l/min, and collector (metal plate) and the distance that goes out between the spinning nozzle are 15cm.The feeding device pump of sodium alginate electrospinning silk stock solution is equipped with in unlatching, and injection stream is ejected on the collector, the electrostatic spinning process stabilization, and (precipitation bath is that mass percent is 10% CaCl on the collector in being immersed in precipitation bath
2The mixed solution of the aqueous solution and dehydrated alcohol, wherein the volume percent of dehydrated alcohol in mixing solutions is 60%) receive tunica fibrosa.
The 4th step: collected tunica fibrosa is soaked 2 hours to remove residual solvent in dehydrated alcohol, and with the continuous drip washing tunica fibrosa of dehydrated alcohol 3 times, at last with tunica fibrosa vacuum-drying after 12 hours in 50 ℃ of vacuum drying ovens, obtain a kind of fully biodegradable of forming by the alginate of 100% component and the micro/nano fibrous membrane material of bio-absorbable, can be used for organizational project and aspects such as drug delivery and beauty treatment material.
Embodiment 4
The first step: with viscosity is that the sodium alginate of 3500 centipoises is a raw material, and properties-correcting agent is glycerine, at normal temperatures sodium alginate is dispersed in the glycerine, and wherein the weightmeasurement ratio of sodium alginate and glycerine is 4g/ml%.
Second step: add aqueous solvent in above-mentioned suspension, wherein the volume ratio of water and glycerine is 1, continues to stir, until the solution of being dissolved into homogeneous transparent.
The 3rd step: the above-mentioned solution of removing bubble that leaves standstill is injected in the electrostatic spinning container, spinning temperature is room temperature (25 ℃), the high-voltage power supply output voltage is 22KV, and feeding rate is 120 μ l/min, and the distance between collector (metal copper mesh) and the spinning nozzle is 10cm.The feeding device pump of sodium alginate electrospinning silk stock solution is equipped with in unlatching, and injection stream is ejected on the collector, the electrostatic spinning process stabilization, and (precipitation bath is that mass percent concentration is 6% CaCl all being immersed in collector in the precipitation bath
2The mixed solution of the aqueous solution and dehydrated alcohol, wherein the volume percent of dehydrated alcohol in mixing solutions is 80%) on receive tunica fibrosa.
The 4th step: collected tunica fibrosa is soaked 2 hours to remove residual solvent in dehydrated alcohol, and with the continuous drip washing tunica fibrosa of dehydrated alcohol 3 times, at last with tunica fibrosa vacuum-drying after 12 hours in 50 ℃ of vacuum drying ovens, obtain a kind of fully biodegradable of forming by the alginate of 100% component and the micro/nano fibrous membrane material of bio-absorbable, can be used for organizational project and aspects such as drug delivery and beauty treatment material.
Embodiment 5
The first step: with viscosity is that the sodium alginate of 3500 centipoises is a raw material, and properties-correcting agent is glycerine, at normal temperatures sodium alginate is dispersed in the glycerine, and wherein the weightmeasurement ratio of sodium alginate and glycerine is 4g/ml%.
Second step: add aqueous solvent in above-mentioned suspension, wherein the volume ratio of water and glycerine is 1, continues to stir, until the solution of being dissolved into homogeneous transparent.
The 3rd step: the above-mentioned solution of removing bubble that leaves standstill is injected in the electrostatic spinning container, and spinning temperature is room temperature (25 ℃), and the high-voltage power supply output voltage is 22KV, and feeding rate is 90 μ l/min, and the distance between collector (metal copper mesh) and the spinning nozzle is 10cm.The feeding device pump of sodium alginate electrospinning silk stock solution is equipped with in unlatching, and injection stream is ejected on the collector, the electrostatic spinning process stabilization, and (precipitation bath is that mass percent concentration is 6% CaCl all being immersed in collector in the precipitation bath
2The mixed solution of the aqueous solution and dehydrated alcohol, wherein the volume percent of dehydrated alcohol in mixing solutions is 80%) on receive tunica fibrosa.
The 4th step: collected tunica fibrosa is soaked 2 hours to remove residual solvent in dehydrated alcohol, and with the continuous drip washing tunica fibrosa of dehydrated alcohol 3 times, at last with tunica fibrosa vacuum-drying after 12 hours in 50 ℃ of vacuum drying ovens, obtain a kind of fully biodegradable of forming by the alginate of 100% component and the micro/nano fibrous membrane material of bio-absorbable, can be used for organizational project and aspects such as drug delivery and beauty treatment material.
Claims (9)
1. the preparation method of a pure sodium alginate nano fiber membrane material is characterized in that, this method may further comprise the steps:
1) the raw material sodium alginate is dispersed in the properties-correcting agent, wherein the weightmeasurement ratio of sodium alginate and properties-correcting agent is 2g/ml%～4g/ml%, and then in above-mentioned mixing solutions, add solvent, wherein the volume ratio of solvent and properties-correcting agent is 0.5～1, after waiting to stir, staticly obtain sodium alginate electrostatic spinning stoste after separating out bubble;
2) the sodium alginate electrospinning silk stock solution that step 1) is obtained is injected in the feeding device of electrostatic spinning apparatus, and the feeding rate of adjusting stoste is 5～300 μ l/min; Distance between the spinning nozzle of feeding device and the collector of ground connection is 5～25cm; Envrionment temperature is 20～70 ℃; The air velocity of environment is 0～8.5m
3/ hr; Open high-voltage power supply, voltage is 1～60kV, opens the feeding device pump that sodium alginate electrospinning silk stock solution is housed, and injection stream is ejected on the collector, but obtains the pure sodium alginate nano fiber membrane material of biodegradable and bio-absorbable on collector;
Described properties-correcting agent is the mixture of glycerine or glycerine and ethylene glycol, and wherein the volume ratio of glycerine and ethylene glycol is 50～100: 50～0.
2. method according to claim 1 is characterized in that: described collector need be fully immersed in when collecting the sodium alginate fiber and contain CaCl
2Precipitation bath in.
3. method according to claim 2 is characterized in that: described precipitation bath is that mass percent concentration is 5%～10% CaCl
2The aqueous solution and the mixed solution of dehydrated alcohol, wherein the volume percent of dehydrated alcohol in mixing solutions is 60～80%.
4. method according to claim 1, it is characterized in that: described step 2) but the pure sodium alginate nano fiber membrane material of obtain biodegradable and bio-absorbable in dehydrated alcohol, soak to remove residual solvent, and with dehydrated alcohol repeatedly the drip washing tunica fibrosa washed away fully until remaining spin solvent, tunica fibrosa after the vacuum-drying, is obtained the pure sodium alginate nano fiber membrane material of the biology of biodegradable and absorption in 20～60 ℃ of vacuum drying ovens.
5. according to claim 1 or 4 described methods, it is characterized in that: described solvent is selected from water or water and ethanol mixed solvent, and wherein water and alcoholic acid volume ratio are 2: 1～3: 1 in the mixed solvent.
6. according to claim 1,2 or 4 described methods, it is characterized in that: the mean diameter of described pure sodium alginate nano fiber is 80nm～1 μ m.
7. method according to claim 1 is characterized in that: the concentration of the raw material sodium alginate in the described sodium alginate electrostatic spinning stoste is 1g/ml%～2.67g/ml%.
8. according to claim 1 or 7 described methods, it is characterized in that: described raw material sodium alginate is at 25 ℃, and mass percent concentration is 2% the soltion viscosity sodium alginate greater than 3500 centipoises.
9. method according to claim 1 is characterized in that: described envrionment temperature is 20～40 ℃; The air velocity of environment is 0.5～5m
3/ hr.
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| CN102071497B (en) * | 2010-12-03 | 2012-05-09 | 北京化工大学 | Preparation method of sodium alginate nanofiber |
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| CN105586716A (en) * | 2014-10-26 | 2016-05-18 | 天津开发区金衫包装制品有限公司 | High-content sodium alginate nanofiber membrane and electrostatic spinning manufacturing method thereof |
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| CN106480517A (en) * | 2015-08-31 | 2017-03-08 | 青岛新智源健康科技有限公司 | A kind of sodium alginate nano fiber and its scale electro spinning method for preparing and application |
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| CN105297153B (en) * | 2015-11-19 | 2017-12-12 | 暨南大学 | A kind of wet spinning device and wet spinning process of electrostatic auxiliary |
| CN105544002B (en) * | 2015-12-18 | 2017-10-20 | 厦门百美特生物材料科技有限公司 | A kind of high water absorption composite fibre and preparation method thereof |
| CN105999367B (en) * | 2016-08-08 | 2019-06-14 | 山东朱氏堂医疗器械有限公司 | A kind of surgery medical dressing and preparation method thereof |
| CN106178080B (en) * | 2016-08-08 | 2019-07-23 | 绍兴瑞凯防护用品有限公司 | A kind of surgery medical dressing hemostatic adhesive bandage |
| CN106421930A (en) * | 2016-11-03 | 2017-02-22 | 常州亚环环保科技有限公司 | Preparation method of nonirritating artificial skin |
| CN106362193A (en) * | 2016-11-07 | 2017-02-01 | 广州润虹医药科技有限公司 | Novel alginate dressing and preparation method thereof |
| CN106592017B (en) * | 2016-11-08 | 2019-02-05 | 青岛大学 | A kind of preparation method of the pure sodium alginate nano fiber based on electrostatic spinning shapes |
| CN109576817A (en) * | 2018-11-12 | 2019-04-05 | 精英塑胶制品有限公司 | A kind of preparation method and nanofiber facial mask of nanofiber facial mask |
| CN114058061B (en) * | 2020-08-03 | 2023-03-28 | 中国海洋大学 | Ultraviolet-proof alginate fiber membrane and preparation method thereof |
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| CN1332081A (en) * | 2001-06-25 | 2002-01-23 | 顺德市高士达建筑装饰材料有限公司 | Manufacture of fireproof composite aluminium-plastic board |
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