CN108853570A - A kind of styptic sponge and preparation method thereof - Google Patents

A kind of styptic sponge and preparation method thereof Download PDF

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Publication number
CN108853570A
CN108853570A CN201810778574.XA CN201810778574A CN108853570A CN 108853570 A CN108853570 A CN 108853570A CN 201810778574 A CN201810778574 A CN 201810778574A CN 108853570 A CN108853570 A CN 108853570A
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sponge
sodium alginate
chitosan
styptic sponge
styptic
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CN108853570B (en
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杨瑞
魏征
谢建
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Puyi (Shanghai) Biotechnology Co.,Ltd.
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Pu Yi (shanghai) Biotechnology Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/08Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • A61L24/0036Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • A61L24/0042Materials resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/04Materials for stopping bleeding

Abstract

The present invention provides a kind of styptic sponge, the styptic sponge includes chitosan, sodium alginate, acetic acid, crosslinking agent and water;The present invention also provides a kind of preparation methods of styptic sponge;Styptic sponge provided by the present invention, using sodium alginate and chitosan as main raw material(s), prepare the sodium alginate-chitosan composite sponge with good haemostatic properties, absorb after a large amount of blood still intensity with higher, compressive load every square centimeter can reach 0.2N or so, vascular compression hemostasis to housing surface, the sponge for absorbing blood or penetrating fluid can also fast degradation, it can most degrade in 1 day fastly, catabolite flows out cavity automatically, compressing both intensity and fast degradation performance is cleverly combined, product is easy to use, and effect is obvious.

Description

A kind of styptic sponge and preparation method thereof
Technical field
The invention belongs to medical instruments field, it is related to a kind of styptic sponge and preparation method thereof.
Background technique
It can not for the treatment of the rich blood vessels cavity bleeding such as ear, nose, since its position is special, the limitation of range of operation Sewing hemostasis is carried out, clogging hemostasis by compression by part becomes maximally efficient and universal method.The purpose of filling is in addition to hemostasis It is experienced with it would also be desirable to be able to more comfortably treat to patient one while preventing adhesion.
Functional ear, postoperative nasal endoscopic are often filled out with the non-degradable material such as vaseline gauze, absorbent cotton, expandable sponges Art chamber is filled in achieve the effect that hemostasis by compression.Although haemostatic effect is good, this kind of material filling time is long, biocompatibility Difference, it is stronger to the sensitive parts irritation such as ear nose the disadvantages of.And after the 12-48h that stops blooding, since this kind of material can not voluntarily drop Solution, needs to take out choke material to hospital.In hemostasis, blood solidify after scab and choke material be tightly adhered to one It rises, easily causes scab to fall off when extracting material out, cause violent feeling of pain and secondary bleeding, for sensitive part such as nose Chamber mucous membrane is likely to occur strong uncomfortable reaction, including headache, nasal obstruction, ear muffle, excessive tear etc..Part is artificial synthesized on the market at present Material has certain fast degradation ability, when being used as hemostasis with packs, can absorb extra oozing of blood and diffusate, itself hair Raw expansion, is bonded wound in narrow cavity and vascular compression reaches anastalsis, and fast degradation can be not necessarily to after hemostasis It is artificial to take out, there is apparent advantage relative to traditional non-degradable material.
But compared to synthetic material, degradable natural biological medical material is in addition to swollen with that can absorb sepage generation The ability of swollen hemostasis by compression and fast degradation, the spies such as there are also biocompatibilities good, biodegradable, absorbable, nontoxic Point is conducive to the growth of granulation tissue, moreover it is possible to play the role of accelerating wound healing.In addition, certain bio-medical materials are also Some special autologous thrombin mechanism such as adsorb platelet aggregation and combine in wound, reach coagulation function.
Chitosan (Chitosan, abbreviation CS) also known as chitin, chitosan, chitosan etc. are by N- amido Portugal For grape sugar with made of β-Isosorbide-5-Nitrae glycosidic bond condensation, it is thin that its raw material chitin (also known as chitin) is that one kind is widely present in fungi Natural polymer in cell wall, insect shell and ocean crustacean.Yield is only second to plant fibre in nature The organic polymer for tieing up element, is a kind of natural regeneration resource extremely abundant.- NH on CS strand2So that CS molecule has Cationic characteristic, the positive charge on the surface CS can be reacted with erythrocyte surface negative electrical charge substance generation electrostatic assembles red blood cell Quickly form blood clot.In addition, CS has certain stimulation to blood platelet, blood platelet is activated rapidly at bleeding initial stage, Platelet surface forms a large amount of electronegativity substances after activation, is assembled with positively charged CS by electrostatic attraction, forms blood clotting Block achievees the purpose that hemostasis.CS can also be used in wound covering, has sterilizing, promotes wound healing, absorb Wound exudate, be not easy The effects of syneresis.Under the action of human enzymes, CS can be degraded into the advantageous substance N-acetyl-glucosamine of human body, this Substance can stimulate wound site to generate hyaluronic acid, promote wound healing and skin regeneration.Chitosan is being sent out due to absorbing acetic acid Proton that scorching position releases and play analgesic effect, dressing made of existing CS can play refrigerant and comfortable when contacting with wound Moisturizing effect, have the good effect of releiving to wound pain.
Sodium alginate (Sodium Alginate, abbreviation SA) is sweet by α-L- guluronic acid (referred to as " G " section) and β-D- The random block linear copolymer for revealing uronic acid (referred to as " M " section) 2 kinds of monomer compositions, by made of Isosorbide-5-Nitrae-glucosides key connection Mucopolysaccharide.In divalent metal (such as Ca2+) in the presence of, G sections can be folded into typical " egg case type structures ", increase molecule Original linear macromolecule is become reticular structure by the interaction force between chain.SA be extracted from brown alga it is natural Polysaccharide has many advantages, such as good biocompatibility, biodegradability, high oxygen permeability, moisture absorption plastic.As one kind derived from plant The natural wound repair material of object is had no adverse reaction, and can treat or substitute body with Wound dressing prepared by SA with body In defective tissue, promote healing.The Wound dressing of SA preparation, in addition to having isolation bacterium, virus, provides and is conducive in application The functions such as the microenvironment of wound healing, the Na in blood and penetrating fluid that wound infiltrates+With Ca2+Exchange reaction occurs, hands over Swap out the Ca come2+It is discharged into induced platelet activation after wound surface, hemostasis growth factor is generated and plays hemostasis and healing acceleration The effects of.
CN105641733A discloses a kind of preparation method of composite antibacterial bleeding-stopping dressing, with chitosan, carboxymethyl chitosan Sugar, sodium alginate are raw material, prepare chitosan solution and carboxymethyl chitosan solution.By chitosan solution or carboxymethyl chitosan After calcium chloride or aldehyde crosslinking agent or plant extract crosslinking agent and betadine antiseptic mixing is added in solution or both solution, The mixed solution of sodium alginate, Sodium Hyaluronate etc. is added in the solution of not formed gel phase, is coated on fibrous absorbent pad or fibre Tie up nonwoven surface, or fibrous absorbent pad or fabric nonwoven cloth be placed in the solution of not formed gel phase be completely soaked to Saturation, by vacuum freeze drying at spongy solid.The antibacterial anti hemorrhagic dressing of method preparation is nontoxic according to this, no heat source, biology Compatibility is high;With inhibiting bacterial growth, prevention bacterium to enter the surface of a wound, promote skin regeneration, it is excellent to reduce scar etc. for healing acceleration Gesture.But the bleeding-stopping dressing that the method is only prepared, without degradable performance.
CN106512073A discloses a kind of preparation method of alginic acid/chitosan blend sponge, which is characterized in that including Following steps:(1) sodium alginate powder is soluble in water, it is molten to be configured to the sodium alginate that weight percent is 0.1%~6% Liquid;Micron or nanoscale slightly solubility calcium salt powder are uniformly mixed with sodium alginate soln, being configured to weight percent is 0.01%~5% calcium salt/sodium alginate suspension;(2) Chitosan powder is dissolved in the acid that volume fraction is 0.25%~3% Property solution in, by weight percentage, be configured to concentration be 0.1%~5% chitosan acid solution, by chitosan acid solution It is slowly added into calcium salt/sodium alginate suspension of step (1), stirs, form alginic acid/chitosan gel rubber suspension;(3) By alginic acid/chitosan gel rubber suspension homogenate, deaeration is freeze-dried to get alginic acid/chitosan blend sponge.But this In method actual mechanical process, be it is very difficult, for insoluble calcium phosphate in the moment for touching acid, calcium salt is dissolved into calcium ion meeting Rapid crossslinked sodium alginate forms insoluble calcium alginate, cannot be with chitosan uniform dissolution;In addition, being dissolved in acid Chitosan solution have a large amount of positive charge, encounter the sodium alginate soln with negative electrical charge, can quickly form cotton-shaped insoluble It is uneven equally to will cause mixing for object;The method must control concentration in extremely low concentration, be possible to that sponge is prepared, It is restricted larger, it is unfavorable for actual production.
CN107296978A discloses a kind of spongy hemostatic material in medical use of organism, and sodium alginate strong oxidizer is acted on Lower oxidation obtains oxidized sodium alginate as crosslinking agent, is added in gelatin/sodium alginate mixed solution, and addition non-ionic surface is living Property agent and softening agent after to obtain gelatin/sodium alginate spongy after the immersion of mechanical foaming, freeze-drying and chitosan solution Hemostatic material in medical use;The strong oxidizer is sodium metaperiodate;The nonionic surfactant be Pluronic F68, The one or more of F108 or F127;The softening agent is glycerine.The hemostatic material of the method preparation, without degradation Advantage, compression support force intensity are lower.
Currently, the existing equal existing defects of styptic sponge, for this reason, it may be necessary to develop, a kind of novel intensity is high, degrades fastly Styptic sponge.
Summary of the invention
The purpose of the present invention is to provide a kind of styptic sponges and preparation method thereof.
In order to achieve that object of the invention, the present invention uses following technical scheme:
In a first aspect, the styptic sponge includes chitosan, sodium alginate, second the present invention provides a kind of styptic sponge Acid, crosslinking agent and water.
Styptic sponge provided by the invention is not related to any toxic crosslinking agent, is main with sodium alginate and chitosan Raw material absorb after a large amount of blood still intensity with higher, and compressive load every square centimeter can reach 0.2N or so, right The vascular compression of housing surface is stopped blooding, absorb blood or penetrating fluid sponge can also fast degradation, can most be dropped in 1 day fastly Solution, catabolite flow out cavity automatically, cleverly combine compressing both intensity and fast degradation performance, and product is easy to use, Effect is obvious.
It preferably, is matter of the sodium alginate in styptic sponge based on 100% by the gross mass percentage of styptic sponge Amount percentage be 0.5%-5%, such as can be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% etc..
In the present invention, the ingredient in addition to sodium alginate, amount is added according to the proportion, and gross mass percentage accounts for 95%-99.5%.
Preferably, the mass ratio of the sodium alginate and chitosan is (16-1):(1-8), such as can be 16:1,15: 1,13:1,10:1,6:1,4:1,1:1,1:2,1:3,1:4,1:5,1:6,1:7 or 1:8.
Preferably, the mass ratio of the sodium alginate and chitosan is (8-1):(1-4).
Preferably, the mass ratio of the sodium alginate and chitosan is (4-1):(1-2).
In the present invention, ionomer mainly is carried out using sodium alginate and calcium ion, chitosan and sodium alginate Electrostatic adsorption carries out preparation sponge for auxiliary, and if the content of sodium alginate is too high, crosslink density is excessively high, degradation Time extends;And if chitosan content is excessively high, it on the one hand needs to be added more acid, on the other hand can reduce hemostasis sea Continuous support strength.
Preferably, the volumetric concentration of the acetic acid is 0.05%-2%, for example, can be 0.05%, 0.1%, 0.15%, 0.18%, 0.2%, 1%, 1.5%, 1.6%, 1.8% or 2% etc., preferably 0.1%-1%.
In the present invention, volumetric concentration of the acetic acid in styptic sponge, which is referred to, mixes according to sodium alginate with chitosan The mixed solution obtained afterwards, after adding acetic acid, acetic acid volumetric concentration shared in chitosan solution.
Preferably, the crosslinking agent is calcium chloride.
Preferably, mass percent of the crosslinking agent in styptic sponge is 0.5%-3%, such as can be 0.5%, 1%, 1.5%, 2%, 2.5% or 3% etc..
Second aspect, the present invention provides a kind of preparation method of styptic sponge as described in relation to the first aspect, the preparations Method includes the following steps:
(1) sodium alginate is mixed in water with chitosan, acetic acid is then added, stir to get sodium alginate mixing Solution;
(2) mixed solution of sodium alginate that step (1) obtains is obtained into dry sponge by freeze-drying, then uses crosslinking agent Immersion obtains the styptic sponge.
It is molten to be first uniformly mixed into sodium alginate neutrality before the reaction by preparation method provided by the invention for chitosan particle In liquid, reduce solution ph by the way that acetic acid is added, while positively charged chitosan particle dissolution with electronegative sodium alginate Polyelectrolyte is formed by electrostatic interaction.Sponge by the way that electrolyte formation is lyophilized has good water imbibition, but in water It is unable to maintain that sponge structure.By the sponge of freeze-drying be placed in cross-linking agent solution (i.e. calcium chloride solution) to sodium alginate in sponge into Row crosslinking enables sponge so that the sodium alginate linear polymeric in freeze-drying electrolyte is cross-linked into sodium alginate network structure A large amount of water suctions are without being dissolved in the water.
In the present invention, when preparing styptic sponge, first mix two kinds of solution, be then lyophilized, after freeze-drying be redissolved calcium salt into Row crosslinking.And be usually first to mix slightly solubility calcium salt in existing method, then using addition acid dissolution chitosan, while dissolving difficulty Dissolubility calcium salt realizes crosslinking, and cross-linking effect is poor, and dissolution is uneven.
Preferably, the time of stirring described in step (1) be 0.5h-3h, such as can be 0.5h, 1h, 1.5h, 2h, 2.5h or 3h etc..
In the present invention, general stirring to chitosan is completely dissolved, so that mixed solution stops stirring in uniform state.
Preferably, the temperature of freeze-drying described in step (2) is 0 DEG C to 10 DEG C, such as can be 0 DEG C, 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C, 7 DEG C, 8 DEG C, 9 DEG C or 10 DEG C etc..
Preferably, the time of freeze-drying described in step (2) be 20h-30h, such as can be 20h, 21h, 22h, 23h, For 24 hours, 25h, 26h, 27h, 28h, 29h or 30h etc..
Preferably, the pre-freeze in grinding tool is needed mixed solution of sodium alginate before being lyophilized described in step (2).
In the present invention, the mixed solution of sodium alginate stirred and evenly mixed is fitted into the grinding tool with sponge shape and carries out in advance Be frozen into type, generally, the molding temperature of pre-freeze is -20 DEG C, when a length of 3-4h.
Preferably, the method for the immersion of crosslinking agent described in step (2) is:Dry sea after impregnating freeze-drying using coagulating bath It is continuous.
Preferably, the time of the immersion is 0.5h-8h.
Preferably, the coagulating bath include by mass percentage 0.1%-5% (such as can be 0.1%, 1%, 1.5%, calcium chloride 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% etc.), 0.5%-4% (such as can be 0.5%, glycerine 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4% etc.), remaining group are divided into 95% ethanol solution.
In the present invention, calcium chloride is in the form of coagulating bath is impregnated, so that Ca2+It is crosslinked into styptic sponge.
In the present invention, glycerine can generally increase the pliability of styptic sponge.
In the present invention, the sponge after crosslinking agent impregnates, by a large amount of dehydrated alcohols carry out cleaning remove remaining calcium from The substances such as son or acetic acid by vacuum condition or air-dry removal ethyl alcohol, obtain dry styptic sponge, specially sodium alginate- Chitosan compound hemostatic sponge.
Preferably, the preparation method of the styptic sponge specifically includes:
It (1) is in mass ratio (16-1) by sodium alginate and chitosan:(1-8) ratio is mixed in water, wherein sea Mass percent of the mosanom in styptic sponge is 0.5%-5%, acetic acid is then added, so that acetic acid is in mixed solution Volumetric concentration is 0.05%-2%, stirs to get mixed solution of sodium alginate;
(2) mixed solution of sodium alginate for obtaining step (1) passes through in -30 DEG C to -10 DEG C pre-freeze 2h-5h, then 0 DEG C dry sponge is obtained to freeze-drying 0.5h-3h at 10 DEG C, is then impregnated using crosslinking agent, obtain the styptic sponge.
Styptic sponge provided by the invention, using the biodegradable medical material of natural biological with special clotting mechanism Material, can be widely applied to pharmaceutical sanitary field, also can be applied in household life, especially in clinical treatment, wound hemostasis Application value with higher.
Compared with the existing technology, the invention has the advantages that:
The present invention provides a kind of fast degradation styptic sponges, using sodium alginate and chitosan as main raw material(s), preparation Sodium alginate-chitosan composite sponge with good haemostatic properties absorbs after a large amount of blood still intensity with higher, Compressive load every square centimeter can reach 0.2N or so, stops blooding to the vascular compression of housing surface, absorbs blood or infiltration The sponge of liquid can also fast degradation, can most degrade in 1 day fastly, catabolite flows out cavity automatically, cleverly combines compressing Both intensity and fast degradation performance, product is easy to use, and effect is obvious.
Detailed description of the invention
Fig. 1 is sponge compression verification map in the specific embodiment of the invention 1.
Fig. 2 is sponge compression verification map in the specific embodiment of the invention 2.
Fig. 3 is sponge compression verification map in the specific embodiment of the invention 3.
Fig. 4 is sponge compression verification map in the specific embodiment of the invention 4.
Fig. 5 is sponge compression verification map in the specific embodiment of the invention 5.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright , the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
2g SA accurately is weighed, is placed it in 100mL distilled water, stirring is until be completely dissolved.Add into above-mentioned SA solution 1g CS makes the concentration 1% (mass percent) of CS, persistently stirs 2h until CS particle is uniformly mixed in SA solution, to mixing 10% acetic acid of 2mL (so that acetic acid final volume concentration is 0.5%) is added in solution, stirs evenly, mixed solution is injected into In grinding tool, -20 DEG C of pre-freeze 3-4h, 0-10 DEG C of vacuum drying obtains freeze-drying sponge for 24 hours.It places it in coagulating bath and impregnates 2 hours Sodium alginate-chitosan composite sponge is obtained, it is 1% that wherein coagulating bath, which contains calcium chloride mass concentration, and glycerol content is 2%, the sponge after a large amount of washes of absolute alcohol crosslinkings removes ethyl alcohol in sponge by the method that baking oven is dried, obtains hemostasis sea It is continuous.
Embodiment 2
4g SA accurately is weighed, is placed it in 100mL distilled water, stirring is until be completely dissolved.Add into above-mentioned SA solution 1g CS makes the concentration 1% (mass percent) of CS, persistently stirs 2h until CS particle is uniformly mixed in SA solution, to mixing 10% acetic acid of 2mL (so that acetic acid final volume concentration is 0.5%) is added in solution, stirs evenly, mixed solution is injected into In grinding tool, -20 DEG C of pre-freeze 3-4h, 0-10 DEG C of vacuum drying obtains freeze-drying sponge for 24 hours.It places it in coagulating bath and impregnates 2 hours Sodium alginate-chitosan composite sponge is obtained, it is 1% that wherein coagulating bath, which contains calcium chloride mass concentration, and glycerol content is 2%, the sponge after a large amount of washes of absolute alcohol crosslinkings removes ethyl alcohol in sponge by the method that baking oven is dried, obtains hemostasis sea It is continuous.
Embodiment 3
2g SA accurately is weighed, is placed it in 100mL distilled water, stirring is until be completely dissolved.Add into above-mentioned SA solution 1g CS makes the concentration 1% (mass percent) of CS, persistently stirs 2h until CS particle is uniformly mixed in SA solution, to mixing 10% acetic acid of 2mL (so that acetic acid final volume concentration is 0.5%) is added in solution, stirs evenly, mixed solution is injected into In grinding tool, -20 DEG C of pre-freeze 3-4h, 0-10 DEG C of vacuum drying obtains freeze-drying sponge for 24 hours.It places it in coagulating bath and impregnates 2 hours Sodium alginate-chitosan composite sponge is obtained, it is 0.1% that wherein coagulating bath, which contains calcium chloride mass concentration, and glycerol content is 2%, the sponge after a large amount of washes of absolute alcohol crosslinkings removes ethyl alcohol in sponge by the method that baking oven is dried, obtains hemostasis sea It is continuous.
Embodiment 4
16g SA accurately is weighed, is placed it in 100mL distilled water, stirring is until be completely dissolved.Into above-mentioned SA solution Add 1g CS, make the concentration 1% (mass percent) of CS, persistently stir 2h until CS particle is uniformly mixed in SA solution, to mixed It closes and 10% acetic acid of 2mL (so that acetic acid final volume concentration is 0.5%) is added in solution, stir evenly, mixed solution is injected Into grinding tool, -20 DEG C of pre-freeze 3-4h, 0-10 DEG C of vacuum drying obtains freeze-drying sponge for 24 hours.It is small to place it in immersion 2 in coagulating bath When obtain sodium alginate-chitosan composite sponge, it is 1% that wherein coagulating bath, which contains calcium chloride mass concentration, and glycerol content is 2%, the sponge after a large amount of washes of absolute alcohol crosslinkings removes ethyl alcohol in sponge by the method that baking oven is dried, obtains hemostasis sea It is continuous.
Embodiment 5
1g SA accurately is weighed, is placed it in 100mL distilled water, stirring is until be completely dissolved.Add into above-mentioned SA solution 8g CS makes the concentration 1% (mass percent) of CS, persistently stirs 2h until CS particle is uniformly mixed in SA solution, to mixing 10% acetic acid of 2mL (so that acetic acid final volume concentration is 0.5%) is added in solution, stirs evenly, mixed solution is injected into In grinding tool, -20 DEG C of pre-freeze 3-4h, 0-10 DEG C of vacuum drying obtains freeze-drying sponge for 24 hours.It places it in coagulating bath and impregnates 2 hours Sodium alginate-chitosan composite sponge is obtained, it is 1% that wherein coagulating bath, which contains calcium chloride mass concentration, and glycerol content is 2%, the sponge after a large amount of washes of absolute alcohol crosslinkings removes ethyl alcohol in sponge by the method that baking oven is dried, obtains hemostasis sea It is continuous.
Comparative example 1
2g SA accurately is weighed, is placed it in 100mL distilled water, stirring is until be completely dissolved.Add into above-mentioned SA solution 1g CS makes the concentration 1% (mass percent) of CS, persistently stirs 2h until CS particle is uniformly mixed in SA solution, to mixing 10% acetic acid of 2mL (so that acetic acid final volume concentration is 0.5%) is added in solution, stirs evenly, mixed solution is injected into In grinding tool, -20 DEG C of pre-freeze 3-4h, 0-10 DEG C of vacuum drying obtains freeze-drying sponge for 24 hours.It places it in coagulating bath and impregnates 2 hours Sodium alginate-chitosan composite sponge is obtained, it is 2% that wherein coagulating bath, which contains glycerol content, and a large amount of washes of absolute alcohol are handed over Sponge after connection removes ethyl alcohol in sponge by the method that baking oven is dried, obtains styptic sponge.
Comparative example 2
2g SA accurately is weighed, is placed it in 100mL distilled water, stirring is until be completely dissolved.Add into above-mentioned SA solution 1g CS makes the concentration 1% (mass percent) of CS, persistently stirs 2h until CS particle is uniformly mixed in SA solution, to mixing 10% acetic acid of 2mL (so that acetic acid final volume concentration is 0.5%) is added in solution, stirs evenly, mixed solution is injected into In grinding tool, -20 DEG C of pre-freeze 3-4h, 0-10 DEG C of vacuum drying obtains freeze-drying sponge for 24 hours.It places it in coagulating bath and impregnates 2 hours Sodium alginate-chitosan composite sponge is obtained, it is 1% that wherein coagulating bath, which contains calcium chloride mass concentration, and a large amount of dehydrated alcohols are clear Sponge after washing crosslinking removes ethyl alcohol in sponge by the method that baking oven is dried, obtains styptic sponge.
Performance test
Styptic sponge prepared by embodiment 1-5 carries out compressive load detection, and method is as follows:Before compressive load detection, sea Continuous sample is cut into 1cm × 1cm × 1cm specification, and after fully absorbing PBS buffer solution, water-absorbing sponge is placed in compression plate up and down, is pressing Before contracting experiment starts, it is ensured that sponge does not stress, no deformation, and sponge is in the state of most original.Entire compression process is in room temperature Under the conditions of, compression speed 10mm/min, 1cm originally are compressed to 0.8cm (the wherein sponge compression verification in embodiment 1-5 Map is as shown in Figs. 1-5),
Styptic sponge prepared by embodiment 1-5 carries out degradation experiment, and method is as follows:Sponge sample is cut into 1cm × 1cm It after × 1cm, is placed in 10mLPBS buffer and is placed under 37 DEG C of isoperibols, every other day change the liquid once, observe and record drop Situation is solved,
Embodiment 1-5 and comparative example 1,2 specific test results are as shown in table 1:
Table 1
By the test result of embodiment 4 and embodiment 5 it is found that the content of sodium alginate and chitosan is unsuitable excessively high, If the excessively high performance that will affect styptic sponge, degradation time extension or compressive load is caused to reduce.Pass through the test of comparative example 1 It is found that calcium chloride is necessary in crosslinking agent, if having lacked Ca2+Sponge can not then be made;It can by the test of comparative example 2 Know, if having lacked glycerine, the hardness of sponge is higher.
The Applicant declares that the present invention is explained by the above embodiments styptic sponge and preparation method thereof of the invention, but The invention is not limited to above-mentioned processing steps, that is, do not mean that the present invention must rely on the above process steps to be carried out.Institute Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of raw material selected by the present invention And addition, selection of concrete mode of auxiliary element etc., all of which fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. a kind of styptic sponge, which is characterized in that the styptic sponge include chitosan, sodium alginate, acetic acid, crosslinking agent and Water.
2. styptic sponge according to claim 1, which is characterized in that by styptic sponge gross mass percentage be 100% Meter, mass percent of the sodium alginate in styptic sponge are 0.5%-5%.
3. styptic sponge according to claim 1 or 2, which is characterized in that the mass ratio of the sodium alginate and chitosan For (16-1):(1-8);
Preferably, the mass ratio of the sodium alginate and chitosan is (8-1):(1-4);
Preferably, the mass ratio of the sodium alginate and chitosan is (4-1):(1-2).
4. styptic sponge according to any one of claim 1-3, which is characterized in that the volumetric concentration of the acetic acid is 0.05%-2%, preferably 0.1%-1%.
5. styptic sponge described in any one of -4 according to claim 1, which is characterized in that the crosslinking agent is calcium chloride;
Preferably, mass percent of the crosslinking agent in styptic sponge is 0.5%-3%.
6. the preparation method of styptic sponge according to any one of claims 1-5, which is characterized in that the preparation method Include the following steps:
(1) sodium alginate is mixed in water with chitosan, acetic acid is then added, it is molten to stir to get sodium alginate mixing Liquid;
(2) mixed solution of sodium alginate that step (1) obtains is obtained into dry sponge by freeze-drying, is then impregnated using crosslinking agent Obtain the styptic sponge.
7. preparation method according to claim 6, which is characterized in that the time of stirring described in step (1) is 0.5h- 3h。
8. preparation method according to claim 6 or 7, which is characterized in that the temperature of freeze-drying described in step (2) is 0 DEG C To 10 DEG C;
Preferably, the time of freeze-drying described in step (2) is 20h-30h;
Preferably, the pre-freeze in grinding tool is needed mixed solution of sodium alginate before being lyophilized described in step (2).
9. preparation method a method according to any one of claims 6-8, which is characterized in that the leaching of crosslinking agent described in step (2) The method of bubble is:The dry sponge after freeze-drying is impregnated using coagulating bath;
Preferably, the time of the immersion is 0.5h-8h;
Preferably, the coagulating bath includes the glycerine of the calcium chloride of 0.1%-5%, 0.5%-4% by mass percentage, Remaining group is divided into 95% ethanol solution.
10. the preparation method according to any one of claim 6-9, which is characterized in that the preparation method specifically includes:
It (1) is in mass ratio (16-1) by sodium alginate and chitosan:(1-8) ratio is mixed, and wherein sodium alginate is only Mass percent in sea of blood silk floss is 0.5%-5%, acetic acid is then added, so that volumetric concentration of the acetic acid in mixed solution is 0.05%-2% stirs to get mixed solution of sodium alginate;
(2) mixed solution of sodium alginate for obtaining step (1) passes through pre-freeze, and 0.5h-3h is then lyophilized at 0 DEG C to 10 DEG C and obtains It to dry sponge, is then impregnated using crosslinking agent, obtains the styptic sponge.
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CN112870429A (en) * 2020-12-28 2021-06-01 天津科技大学 Chitosan-based polyelectrolyte composite hemostatic sponge, preparation method and application
CN115089760A (en) * 2022-07-15 2022-09-23 中国科学院长春应用化学研究所 Antibacterial hemostatic sponge for deep wound hemorrhage and preparation method thereof
CN115779136A (en) * 2022-12-15 2023-03-14 湖南中腾湘岳生物科技有限公司 Medical hemostatic material and preparation method thereof
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CN116144068A (en) * 2022-12-20 2023-05-23 武夷学院 Preparation method and application of alkylated chitosan/sodium alginate composite sponge material
CN116144068B (en) * 2022-12-20 2024-04-23 武夷学院 Preparation method and application of alkylated chitosan/sodium alginate composite sponge material

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