CN107376005A - A kind of biodegradable medical hemostatic paper and preparation method thereof - Google Patents
A kind of biodegradable medical hemostatic paper and preparation method thereof Download PDFInfo
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- CN107376005A CN107376005A CN201710662857.3A CN201710662857A CN107376005A CN 107376005 A CN107376005 A CN 107376005A CN 201710662857 A CN201710662857 A CN 201710662857A CN 107376005 A CN107376005 A CN 107376005A
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- sodium alginate
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- medical hemostatic
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- 230000002439 hemostatic effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000661 sodium alginate Substances 0.000 claims abstract description 66
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 66
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 66
- 229920000159 gelatin Polymers 0.000 claims abstract description 20
- 235000019322 gelatine Nutrition 0.000 claims abstract description 20
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims abstract description 20
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims abstract description 20
- 108010010803 Gelatin Proteins 0.000 claims abstract description 18
- 239000008273 gelatin Substances 0.000 claims abstract description 18
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000017 hydrogel Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 39
- 238000007254 oxidation reaction Methods 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 238000013019 agitation Methods 0.000 claims description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 31
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 15
- 235000011187 glycerol Nutrition 0.000 claims description 15
- 239000001110 calcium chloride Substances 0.000 claims description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 230000001954 sterilising effect Effects 0.000 claims description 12
- 238000004659 sterilization and disinfection Methods 0.000 claims description 12
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 claims description 11
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000001828 Gelatine Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 229940014259 gelatin Drugs 0.000 claims 2
- 229920005615 natural polymer Polymers 0.000 claims 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 230000023597 hemostasis Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000001356 surgical procedure Methods 0.000 abstract description 3
- 238000005213 imbibition Methods 0.000 abstract description 2
- 230000000638 stimulation Effects 0.000 abstract description 2
- 206010070834 Sensitisation Diseases 0.000 abstract 1
- 229940030225 antihemorrhagics Drugs 0.000 abstract 1
- 230000000025 haemostatic effect Effects 0.000 abstract 1
- 208000014674 injury Diseases 0.000 abstract 1
- 231100001083 no cytotoxicity Toxicity 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 230000008313 sensitization Effects 0.000 abstract 1
- 230000008733 trauma Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000003643 water by type Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 12
- 239000004568 cement Substances 0.000 description 11
- 230000003068 static effect Effects 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000000499 gel Substances 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000515 collagen sponge Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 102000005525 fibrillarin Human genes 0.000 description 1
- 108020002231 fibrillarin Proteins 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- SYUXAJSOZXEFPP-UHFFFAOYSA-N glutin Natural products COc1c(O)cc2OC(=CC(=O)c2c1O)c3ccccc3OC4OC(CO)C(O)C(O)C4O SYUXAJSOZXEFPP-UHFFFAOYSA-N 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000003612 virological effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/009—Materials resorbable by the body
-
- 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0023—Polysaccharides
-
- 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0028—Polypeptides; Proteins; Degradation products thereof
- A61L26/0038—Gelatin
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/04—Materials for stopping bleeding
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Medicinal Preparation (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a kind of biodegradable medical hemostatic paper and preparation method thereof.Using hydroxymethyl cellulose, sodium alginate, hydrogel is made after a certain degree of crosslinking in the material such as oxidized sodium alginate and gelatin, is dried in dehydrofreezing and is squeezed into scraps of paper shape.Biodegradable medical hemostatic patch has preferable water imbibition and water resistance, while has excellent mechanical property.No cytotoxicity, has no stimulation of the skin and sensitization, has quick-acting haemostatic powder effect, available for surgery and the local hemostasis of trauma patient.
Description
Technical field
This experiment invention is related to a kind of biodegradable medical hemostatic paper and preparation method thereof, belongs to bio-medical material neck
Domain.
Background technology
The present invention relates to biological hemostatic patch a kind of degradable and with excellent hemostatic function.Specifically use
After natural medical polymer crosslinking, it is freeze-dried, is crushed to, available for surgery and the local hemostasis of wounded patient.
There is very big requirement to local hemostasis in clinical and real life, timely hemostasis contributes to us to avoid carefully
Bacterium, viral situations such as infecting.In Clinical Surgery, help to reduce patient's blood transfusion so as to reduce the chance of infection.It is clinical at present and
There are some commercial prods to come into operation in real life.Some traditional hemostatic materials have more shortcoming, such as, it is fine
Fibrillarin glue anastalsis is good, but it is obvious to configure complex and inflammation.Collagen sponges are made up of foreign protei, office
Portion's inflammatory reaction is also particularly evident.Preferable hemostatic material should meet multinomial requirement：It is non-toxic to human body first, have no stimulation
And good biocompatibility.There is good Bioabsorbable simultaneously, be easy to process, there is certain mechanical property.
Hydroxymethyl cellulose is that a kind of etherified reaction of cellulosic molecule introduces soluble derivative obtained from methylol.
The introducing of methylol improves the water solubility of cellulosic molecule, while it has good film forming, biocompatibility, nontoxic nothing
Evil, is widely used in field of medicaments.Gelatin is the high dimerization of the partially hydrolysed obtained high-molecular polypeptide of the collagen of animal
Compound, collagen can typically extract from the skin of animal, bone, cartilage, ligament, sarolemma etc..Its gelation, retentiveness, film forming
Property, biocompatibility are very excellent, have been widely used for the industries such as food, medical science, chemical industry.2015, Liu Yong et al. public affairs
A kind of preparation method (patent No. of chitosan medical biological antibacterial dressing is opened：CN201310463753.1), shell is gathered first
Sugar is dissolved in acid solution and carboxymethyl chitosan is dissolved in water and is configured to chitosan solution and carboxymethyl chitosan solution, adds penta 2 afterwards
The aldehyde crosslinking agents such as aldehyde make each self-crosslinking of above-mentioned solution, and finally by coating, biocompatibility height is prepared in freeze-drying, can be with
The medical dressing of effective bacteria growing inhibiting.But crosslinking agent uses the aldehyde crosslinking agents such as glutaraldehyde, there is certain toxicity to human body,
Potential safety hazard be present, do not meet green theory.This patent uses oxidized sodium alginate, and sodium alginate is through sodium periodate oxidation
Obtained oxidized sodium alginate can not only improve the solubility property of sodium alginate, the dialdehyde that simultaneous oxidation sodium alginate obtains afterwards
Schiff reaction can occur with the amino on gelatin for base, chemical crosslinking structure be formed, so as to instead of formaldehyde, glutaraldehyde etc.
Poisonous aldehyde crosslinking agent.
The present invention is appropriately crosslinked by above-mentioned substance.Enough gel strengths and suitable crosslink density ensure that the suction of finished product
Water-based and mechanical strength.The use of Freeze Drying Technique ensure that the porous of gel.Hemostatic adhesive bandage is made after finished product processing and packing,
With preferable mechanical strength.
The content of the invention
The purpose of the present invention is to obtain a kind of biodegradable aerogel dressing, at the same reach must intensity,
With preferable water imbibition and water resistance, soak do not change its structure in deionized water, while there is hemostasia effect.Described
Biodegradable hydrogel material, using partial oxidation sodium alginate/sodium alginate/glutin/hydroxymethyl cellulose as matrix.For reality
Existing above-mentioned target, is adopted the following technical scheme that：
(1) prepared by partial oxidation sodium alginate.Sodium alginate is configured to 1wt%~5wt% solution, adds high iodine
Sour sodium solid lucifuge reacts 24~48h, adds ethylene glycol, NaCl stops reaction, precipitating, the filtering drying at 30~60 DEG C；
(2) preparation of sodium alginate/hydroxymethyl cellulose/gelatin cross-blend solution：Weigh sodium alginate 1.0wt%~
5.0wt%, gelatin 1.0wt%~5.0wt%, hydroxymethyl cellulose 1.0wt%~5.0wt%.Add in deionized water, magnetic force
Stirring, dissolves at 20 DEG C~60 DEG C.
(3) toughener 1,2- propane diols and glycerine 6wt%~12wt% are weighed altogether.Add the solution that (2) have dissolved
In, magnetic agitation, normal-temperature dissolution.
(4) the partial oxidation sodium alginate 0.5wt%~3wt% for weighing step (1) preparation adds step (3) described system
In, magnetic agitation, until partial oxidation sodium alginate dissolves, filtering, eliminate bubble.Afterwards with calcium chloride weak solution spray 3~4
It is secondary, stand a period of time.
(5) uniform rubber cement is made in colloid made of above-mentioned steps in homogenizer.Mould is poured into, in -10 DEG C~-40 DEG C ice
6~24h of precooling in case.Is freeze-dried finally with appropriate pressure compaction into paper chip solid with freeze drier afterwards.Disappear
Poison, packaging.As gained biological hemostatic patch.
Specifically, the molecular weight of sodium alginate is 20000~200000g/mol, and the molecular weight of hydroxymethyl cellulose is
20000~200000g/mol, gelatine molecular weight are 20000~200000g/mol.
Specifically, sodium alginate and oxidizing agent sodium periodate and mol ratio are 1:1~2.
Specifically, 1, the mass ratio of 2 propane diols and glycerine is 1:1~5.
Specifically, calcium chloride solution concentration is 1wt%~5wt%.
Specifically.It is -40 DEG C~80 DEG C, cooling time 12~48h that freeze drier, which freezes parameter, 1~10 × 10-3MBr。
Embodiment
The present invention can be illustrated with following example, but be not limited to following Examples.
Embodiment 1
(1) weigh in the balance and take sodium alginate 1.9g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 1.5g, hydroxymethyl cellulose 1.5g, gelatin 3.0g and is added to 85.5g deionized waters
In, the magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 1.70g1,2- propane diols and 5.30g glycerine are weighed, adds the system that step (2) obtains, stirring is completely molten
Solution.The made partial oxidation sodium alginate of 1.5g steps (2) is weighed, normal temperature magnetic agitation is until partial oxidation sodium alginate is complete
Dissolve and system is without layering.After eliminating bubble, 3 to 4 above-mentioned systems are sprayed with 2wt% calcium chloride weak solution, place 4h, system
Into hydrogel.
(4) uniform rubber cement is made in homogenizer.Mould is poured into, uses freeze drier after precooling in -30 DEG C of refrigerators
48h, which is freezed, at -50 DEG C obtains spongy solid.Finally pressurizeed with appropriate pressure into scraps of paper type.With the sterilization of cobalt -60, bag
Dress.
Embodiment 2
(1) weigh in the balance and take sodium alginate 1.9g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 0.6g, hydroxymethyl cellulose 2.4g, gelatin 1.2g and is added to 82.6g deionized waters
In, the magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 3.0g1,2- propane diols and 9.0g glycerine are weighed, adds the system that step (2) obtains, stirring is completely dissolved.
The made partial oxidation sodium alginate of 1.2g steps (2) is weighed, normal temperature magnetic agitation is until partial oxidation sodium alginate is completely molten
Solve and system is without layering.After eliminating bubble, 3 to 4 above-mentioned systems are sprayed with 2wt% calcium chloride weak solution, 4h is placed, is made
Hydrogel.
(4) uniform rubber cement is made in homogenizer.Mould is poured into, uses freeze drier after precooling in -30 DEG C of refrigerators
48h, which is freezed, at -50 DEG C obtains spongy solid.Finally pressurizeed with appropriate pressure into scraps of paper type.With the sterilization of cobalt -60, bag
Dress.
Embodiment 3
(1) weigh in the balance and take sodium alginate 1.9g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 0.8g, hydroxymethyl cellulose 2.1g, gelatin 2.1g and is added to 83.6g deionized waters
In, the magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 1.75g1,2- propane diols and 7.84g glycerine are weighed, adds the system that step (2) obtains, stirring is completely molten
Solution.The made partial oxidation sodium alginate of 1.8g steps (2) is weighed, normal temperature magnetic agitation is until partial oxidation sodium alginate is complete
Dissolve and system is without layering.After eliminating bubble, 3 to 4 above-mentioned systems are sprayed with 2wt% calcium chloride weak solution, place 4h, system
Into hydrogel.
(4) uniform rubber cement is made in homogenizer.Mould is poured into, uses freeze drier after precooling in -30 DEG C of refrigerators
48h, which is freezed, at -50 DEG C obtains spongy solid.Finally pressurizeed with appropriate pressure into scraps of paper type.With the sterilization of cobalt -60, bag
Dress.
Embodiment 4
(1) weigh in the balance and take sodium alginate 1.9g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 1.2g, hydroxymethyl cellulose 2.4g, gelatin 2.4g and is added to 84.5g deionized waters
In, the magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 1.60g1,2- propane diols and 6.40g glycerine are weighed, adds the system that step (2) obtains, stirring is completely molten
Solution.The made partial oxidation sodium alginate of 1.5g steps (2) is weighed, normal temperature magnetic agitation is until partial oxidation sodium alginate is complete
Dissolve and system is without layering.After eliminating bubble, 3 to 4 above-mentioned systems are sprayed with 2wt% calcium chloride weak solution, place 4h, system
Into hydrogel.
(4) uniform rubber cement is made in homogenizer.Mould is poured into, uses freeze drier after precooling in -30 DEG C of refrigerators
48h, which is freezed, at -50 DEG C obtains spongy solid.Finally it is press-formed with appropriate pressure.With the sterilization of cobalt -60, packaging.
Embodiment 5
(1) weigh in the balance and take sodium alginate 1.9g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 1.2g, hydroxymethyl cellulose 2.4g, gelatin 2.4g and is added to 81.6g deionized waters
In, the magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 2.0g1,2- propane diols and 8.0g glycerine are weighed, adds the system that step (2) obtains, stirring is completely dissolved.
The made partial oxidation sodium alginate of 2.4g steps (2) is weighed, normal temperature magnetic agitation is until partial oxidation sodium alginate is completely molten
Solve and system is without layering.After eliminating bubble, 3 to 4 above-mentioned systems are sprayed with 2wt% calcium chloride weak solution, 4h is placed, is made
Hydrogel.
(4) uniform rubber cement is made in homogenizer.Mould is poured into, uses freeze drier after precooling in -30 DEG C of refrigerators
48h, which is freezed, at -50 DEG C obtains spongy solid.Finally pressurizeed with appropriate pressure into scraps of paper type.With the sterilization of cobalt -60, bag
Dress.
Embodiment 6
(1) weigh in the balance and take sodium alginate 1.9g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 0.6g, hydroxymethyl cellulose 1.8g, gelatin 1.8g and is added to 84.4g deionized waters
In, the magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 1.75g1,2- propane diols and 7.85g glycerine are weighed, adds the system that step (2) obtains, stirring is completely molten
Solution.Weigh 1.8g steps (2) made partial oxidation sodium alginate and 3.0g polyethylene glycol dimethacrylates, normal temperature magnetic force
Stirring is until partial oxidation sodium alginate is completely dissolved and system is without layering.After eliminating bubble, with 2wt% calcium chloride weak solution
3 to 4 above-mentioned systems are sprayed, 4h is placed, hydrogel is made.
(4) uniform rubber cement is made in homogenizer.Pour into mould, in -30 DEG C of refrigerators freezing after with freeze drier -
50 DEG C of freezing 48h obtain spongy solid.Finally pressurizeed with appropriate pressure into scraps of paper type.With the sterilization of cobalt -60, packaging.
Embodiment 7
(1) weigh in the balance and take sodium alginate 1.90g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 1.5g, hydroxymethyl cellulose 3g, gelatin 3g and is added in 79.5g deionized waters,
Magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 2.0g1,2- propane diols and 8.0g glycerine are weighed, adds the system that step (2) obtains, stirring is completely dissolved.
3.0g steps (2) made partial oxidation sodium alginate is weighed, normal temperature magnetic agitation is until partial oxidation sodium alginate is completely dissolved
And system is without layering.After eliminating bubble, 3 to 4 above-mentioned systems are sprayed with 2wt% calcium chloride weak solution, 4h is placed, water is made
Gel.
(4) uniform rubber cement is made in homogenizer.Mould is poured into, freeze drier is used after freezing in -30 DEG C of refrigerators
48h, which is freezed, at -50 DEG C obtains spongy solid.Finally pressurizeed with appropriate pressure into scraps of paper type.With the sterilization of cobalt -60, bag
Dress.
Embodiment 8
(1) weigh in the balance and take sodium alginate 1.90g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 1.5g, hydroxymethyl cellulose 3g, gelatin 3g and is added in 77.5g deionized waters,
Magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 3.0g1,2- propane diols and 9.0g glycerine are weighed, adds the system that step (2) obtains, stirring is completely dissolved.
3.0g steps (2) made partial oxidation sodium alginate is weighed, normal temperature magnetic agitation is until partial oxidation sodium alginate is completely dissolved
And system is without layering.After eliminating bubble, 3 to 4 above-mentioned systems are sprayed with 2wt% calcium chloride weak solution, 4h is placed, water is made
Gel.
(4) uniform rubber cement is made in homogenizer.Mould is poured into, freeze drier is used after freezing in -30 DEG C of refrigerators
48h, which is freezed, at -50 DEG C obtains spongy solid.Finally pressurizeed with appropriate pressure into scraps of paper type.With the sterilization of cobalt -60, bag
Dress.
Embodiment 9
(1) weigh in the balance and take sodium alginate 1.90g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 1.5g, hydroxymethyl cellulose 3g, gelatin 3g and is added in 78.4g deionized waters,
Magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 3.0g1,2- propane diols and 9.0g glycerine are weighed, adds the system that step (2) obtains, stirring is completely dissolved.
2.1g steps (2) made partial oxidation sodium alginate is weighed, normal temperature magnetic agitation is until partial oxidation sodium alginate is completely dissolved
And system is without layering.After eliminating bubble, 3 to 4 above-mentioned systems are sprayed with 2wt% calcium chloride weak solution, 4h is placed, water is made
Gel.
(4) uniform rubber cement is made in homogenizer.Mould is poured into, freeze drier is used after freezing in -30 DEG C of refrigerators
48h, which is freezed, at -50 DEG C obtains spongy solid.Finally pressurizeed with appropriate pressure into scraps of paper type.With the sterilization of cobalt -60, bag
Dress.
Embodiment 10
(1) weigh in the balance and take sodium alginate 1.90g to be added in 150g deionized waters, magnetic agitation has dissolved at 30 DEG C
Entirely, 1.76g sodium metaperiodate solids, lucifuge reaction 48h are added, temperature is not higher than 30 DEG C, adds 0.41g ethylene glycol terminating reactions,
150g ethanol is added, 3.0g sodium chloride, static layering, is filtered, is put into 40 DEG C of vacuum drying oven and dries 48h.Oxidation sea is made
Mosanom.
(2) balance measures sodium alginate 0.6g, hydroxymethyl cellulose 1.8g, gelatin 1.8g and is added to 84.0g deionized waters
In, the magnetic agitation at 40 DEG C, until being completely dissolved.
(3) 3.0g1,2- propane diols and 9.0g glycerine are weighed, adds the system that step (2) obtains, stirring is completely dissolved.
0.8g steps (2) made partial oxidation sodium alginate is weighed, normal temperature magnetic agitation is until partial oxidation sodium alginate is completely dissolved
And system is without layering.After eliminating bubble, 3 to 4 above-mentioned systems are sprayed with 2wt% calcium chloride weak solution, 4h is placed, water is made
Gel.
(4) uniform rubber cement is made in homogenizer.Mould is poured into, freeze drier is used after freezing in -30 DEG C of refrigerators
48h, which is freezed, at -50 DEG C obtains spongy solid.Finally pressurizeed with appropriate pressure into scraps of paper shape.With the sterilization of cobalt -60, bag
Dress.
Claims (5)
- A kind of 1. biodegradable medical hemostatic paper and preparation method thereof, it is characterised in that：Using pure natural polymer substance as base Body, biodegradable hydrogel is cross-linked under crosslinking agent, toughener effect, is processed through dehydration and sterilization is made；Described Pure natural polymer substance includes hydroxymethyl cellulose, sodium alginate, gelatin and its bioprotein material；Crosslinking agent is oxidation sea Mosanom and calcium chloride；Toughener includes glycerine and 1,2- propane diols.
- 2. according to described a kind of biodegradable medical hemostatic paper in claim 1 and preparation method thereof, it is characterised in that： The weight/mass percentage composition of each component is：(1) partial oxidation sodium alginate 0.5wt%~3wt%Sodium alginate 1.0wt%~5.0wt%Gelatin 1.0wt%~5.0wt%Hydroxymethyl cellulose 1.0wt%~5.0wt%；(2) toughener 1,2-PD and glycerol content 6wt%~12wt%, its mass ratio are 1:1~5；(3) surplus is water.
- 3. according to described a kind of biodegradable medical hemostatic paper in claim 1 and preparation method thereof, its preparation process For：(1) sodium alginate is configured to 1wt%~5wt% solution, sodium metaperiodate solid lucifuge is added and reacts 24~48h, Add ethylene glycol, NaCl stops reaction, precipitating, the filtering drying at 30~60 DEG C；(2) weigh sodium alginate, gelatin, hydroxymethyl cellulose to add in deionized water, magnetic agitation is molten at 20 DEG C~60 DEG C Solution, 1,2-PD and glycerine are added in solution, normal-temperature dissolution；Weigh partial oxidation sodium alginate, magnetic agitation to portion Divide oxidized sodium alginate dissolving, filter and sprayed 3~4 times with calcium chloride weak solution after eliminating bubble, stood for a period of time；(3) solution is put into 12~48h of freezing in freeze drier after -10 DEG C~-40 DEG C 6~24h of precooling, obtains biology Degradable medical hemostatic adhesive bandage, wherein lyophilized parameter is -40 DEG C~-60 DEG C, 1~10 × 10-3MBr；(4) paper chip solid will be compacted into appropriate pressure；(5) the biodegradable medical hemostatic patch of gained is passed through into the sterilization treatment of cobalt -60.
- 4. according to described a kind of biodegradable medical hemostatic paper in claim 3 and preparation method thereof, it is characterised in that： The molecular weight for the sodium alginate told in step (1) is 20000~200000g/mol；Gelatine molecular weight be 20000~ 200000g/mol；The molecular weight of hydroxymethyl cellulose is 20000~200000g/mol.
- 5. according to a kind of preparation method of described biodegradable medical hemostatic paper in claim 3, it is characterised in that：Step Suddenly sodium alginate and oxidizing agent sodium periodate and mol ratio are 1 in (1):1~2；Calcium chloride solution concentration is 1wt%~5wt%.
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