CN100341933C - Carboxymerhyl chitosan sponge with water-absorbent dilatability and its preparation method and use thereof - Google Patents
Carboxymerhyl chitosan sponge with water-absorbent dilatability and its preparation method and use thereof Download PDFInfo
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- CN100341933C CN100341933C CNB2005100245033A CN200510024503A CN100341933C CN 100341933 C CN100341933 C CN 100341933C CN B2005100245033 A CNB2005100245033 A CN B2005100245033A CN 200510024503 A CN200510024503 A CN 200510024503A CN 100341933 C CN100341933 C CN 100341933C
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Abstract
The present invention discloses carboxymethyl chitosan sponge with water absorption expansion performance, and a preparation method and the application thereof. The sponge uses carboxymethyl chitosan as a main raw material. The preparation method comprises the processes that a small amount of chitosan powder or chitin powder is added to a carboxymethyl chitosan water solution, and a certain amount of glycerol is assisted and is used as a plasticizing agent; 100 ml of solution comprises 1 to 5g of carboxymethyl chitosan, 0.5 to 2g of chitosan powder or chitin powder and 1 to 5g of glycerol; after the solution is stirred and foamed, an environmental protection type ion crosslinking agent is added to the solution and is sufficiently crosslinked, and the solution is frozen and dried. The sponge produced by the technology uses water-soluble substances as raw materials, an acid solvent is avoided to be used, and consequently, the sponge has the significance of environmental protection; the non aldehyde group ion crosslinking agent is adopted, the residual toxicity of an aldehyde group is avoided, and consequently, the sponge has the characteristics of safety and nontoxicity. Moreover, the sponge prepared by the technology has the advantages of softness, high elasticity, strong water absorption expansion capability and rapid hemostasis, and has the functions of bacteriostasis and wound healing promotion. The sponge can be used for the medical fields of surgical hemostasis, cavity channel hemostasis, wound healing, etc.
Description
One, technical field:
The present invention relates to a kind of new bio sponge, specifically is solubility, degradability, the sponge with water-swelling property and the method for making and the purposes of main raw material preparation with the cm-chitosan.
Two, background technology:
At present, on China medical market, there are thirties kinds of medical sponge products to be widely used in surgical hemostasis, cavity hemostasis and wound healing treatment.They mainly all form with material preparations such as gelatin, collagen proteins, because of its raw material is a foreign protein, retain in the human body, easily cause immunogenic response.Chitosan class material is a natural biologic material, can be degraded to the glucosamine of safety non-toxic in human body, also can not cause immunogenic response, thereby has good biocompatibility; Chitosan is the unique positively charged glucosamine of occurring in nature simultaneously, because of its unique physics and chemistry structure, make the chitosan material can by and erythrocyte membrane between charge effect aggegation red corpuscle stop blooding, and hemostatic mechanism need not depend on clotting mechanism, so can also mediate solidifying of heparinization patient blood, this has unique effect for hemostasis in the surgical operation.In addition, chitosan also has antibacterial, as to promote wound healing performance.
Yet chitosan can not dissolve in neutral aqueous solution, and foam performance is not good enough, often needs it is dissolved in the acidic solution with its preparation sponge, treats to regulate pH value again, operations such as washing after sponge is shaped.A kind ofly dissolve chitosan as disclosing among the patent CN1071587A, and after mixing collagen, prepare the production technique of sponge with formaldehyde crosslinking with acetate; Disclose a kind of pastille chitosan-collagen sponge that is used for gynaecopathia as patent CN1431021A, its preparation technology comprises with hydrochloric acid or acetate dissolution chitosan, uses glutaraldehyde cross-linking, after the lyophilize with distilled water wash and vacuum-drying once more.Acidic solution is adopted in chitosan class sponge preparation in the past, easily environmental protection impacted, and the aldehydes linking agent that adopts, easily residual toxicity.
Three, summary of the invention:
The sponge that the present invention is prepared, the cm-chitosan of selecting for use are a kind of water-soluble chitosan derivative, and it can be dissolved in the neutral water well, can dissolve down at physiological condition (pH=6～8), and absorb a large amount of liquid.In addition, as the Amphiphatic high polymer material, it has unique gellifying property under certain conditions, polyvalent ion generation ionomers such as energy and aluminium, calcium, iron.Therefore, we can utilize ionomer mechanism under the condition of gentleness, it is prepared into the cavernous body with satisfactory texture, and needn't be with residual deleterious linking agents such as formaldehyde in a large amount of solvent treatment cavernous bodies.
In addition, the sponge of the present invention preparation also has particular performances, promptly can water-swelling, and make in the cavity hemostasis and except that the anastalsis of biomaterial itself, also can play mechanical pressure hematostatic effect, make anastalsis more definite.
One of technical problem to be solved by this invention provides a kind of carboxymerhyl chitosan sponge with water-swelling property.
Two of technical problem to be solved by this invention provides a kind of preparation technology of carboxymerhyl chitosan sponge.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of carboxymerhyl chitosan sponge, adopt the carboxymethyl chitosan sugar aqueous solution to make, the aqueous solution comprises cm-chitosan, chitosan powder or chitin powder, glycerol plasticizer and environment-friendly type ion crosslinking agent.This cm-chitosan is N, the O-cm-chitosan (N, O-CMC), its molecular structure is as follows,
Wherein the substituting group on the N is at NHCOCH
3Kharophen, NCH
2COOH carboxymethylamino, NH
2Choose a kind of in the amino.Annotate: the group NCH in the molecular structural formula in the round bracket
2COOH is carboxymethylamino, NH
2Be amino, indicate, represent that this group is alternative with round bracket.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows:
(1) the carboxymethyl chitosan sugar aqueous solution comprises cm-chitosan, chitosan powder or chitin powder, glycerol plasticizer and environment-friendly type ion crosslinking agent, make in every 100ml solution and contain cm-chitosan 1～5g, chitosan powder or chitin powder 0.5～2g, glycerine 1～5g, mix under 50 ℃, that the foaming back adds the environment-friendly type ion crosslinking agent under the room temperature is full cross-linked ,-20 ℃ of abundant freezing shaping postlyophilizations 24 hours.The gained cavernous body is cut into required size, shape.
(2) employed environment-friendly type ion crosslinking agent is to choose any one kind of them in water-soluble aluminum salt, calcium salt, the molysite among the above-mentioned preparation technology, and concentration is 1～20%.
The invention has the advantages that:
1, utilizes the cm-chitosan good water-solubility, directly, avoided using the acid leach solution chitosan, have environment protection significance with deionized water preparation sponge slurry; Utilize carboxymethyl electronegative on the cm-chitosan and ion crosslinking agent to carry out ionomer, avoided poisonous linking agents such as use formaldehyde, overcome the shortcoming of residual toxicity in human body easily; And saved last handling processes such as neutralization, washing, and improved security of products, reduced production cost.
2, the sponge of this explained hereafter can form gel rapidly in body fluid, is used for medical field, can form the heavy-gravity protective membrane at the surface of a wound, and haemostatic effect is definite, rapid, but also has good water-swelling property, is specially adapted to the cavity hemostasis.
3, the sponge of this explained hereafter has solubility and biological degradability, can stay in the body and need not second operation and take out.
Four, embodiment:
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1
1% carboxymethyl chitosan sugar aqueous solution 100ml, add 100 order chitin powder 1.0g and glycerine 1ml, 50 ℃ mix the following foaming of back room temperature condition 30 minutes, and adding 1% liquor alumini chloridi 15ml simultaneously carries out crosslinked, pack in the mould-20 ℃ of abundant freezing shapings then into.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 2
2% carboxymethyl chitosan sugar aqueous solution 100ml adds 100 order chitin powder 2g and glycerine 5ml, and 50 ℃ mix, and down foaming 30 minutes of room temperature condition adds 20% liquor alumini chloridi 1ml simultaneously and carries out crosslinkedly, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 3
2% carboxymethyl chitosan sugar aqueous solution 100ml adds 100 order chitosan powder 0.5g and 1ml glycerine, foams 30 minutes, adds 1% calcium chloride solution 5ml simultaneously, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 4
4% carboxymethyl chitosan sugar aqueous solution 100ml adds 100 order chitosan powder 0.5g and glycerine 1ml, foams 30 minutes, adds 20% calcium chloride solution 3ml simultaneously, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 5
5% carboxymethyl chitosan sugar aqueous solution 100ml adds 100 order chitosan powder 2g and glycerine 3ml, foams 30 minutes, adds 10% calcium chloride solution 5ml simultaneously, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 6
4% carboxymethyl chitosan sugar aqueous solution 100ml adds 100 order chitin powder 0.5g and glycerine 2ml, foams 30 minutes, adds 1% ferric chloride Solution 10ml simultaneously, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 7
4% carboxymethyl chitosan sugar aqueous solution 100ml adds 100 order chitosan powder 0.5g and glycerine 1ml, foams 30 minutes, adds 10% ferric chloride Solution 10ml simultaneously, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 8
3% carboxymethyl chitosan sugar aqueous solution 100ml adds chitosan powder 1g and glycerine 4ml, and 50 ℃ mix, and room temperature condition foaming 30 minutes down adds 20% ferric chloride Solution 3ml simultaneously and carries out crosslinkedly, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 9
4% carboxymethyl chitosan sugar aqueous solution 100ml adds 100 order chitosan powder 1.5g and glycerine 3ml, foams 30 minutes, adds 5% ferric chloride Solution 5ml simultaneously, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 10
3% carboxymethyl chitosan sugar aqueous solution 100ml adds 100 order chitin powder 1.5g and glycerine 4ml, and 50 ℃ mix, and down foaming 30 minutes of room temperature condition adds 10% liquor alumini chloridi 5ml simultaneously and carries out crosslinkedly, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Embodiment 11
5% carboxymethyl chitosan sugar aqueous solution 100ml adds 100 order chitosan powder 0.8g and glycerine 3ml, foams 30 minutes, adds 5% liquor alumini chloridi 5ml simultaneously, and in the mould of packing into then ,-20 ℃ freezing 24 hours.After the taking-up, the demoulding and lyophilize at once 24 hours.The gained cavernous body is cut into required size.
Claims (5)
1. the carboxymerhyl chitosan sponge that has water-swelling property; adopt the carboxymethyl chitosan sugar aqueous solution to make; the aqueous solution comprises cm-chitosan, chitosan powder or chitin powder, glycerol plasticizer and environment-friendly type ion crosslinking agent; it is characterized in that: cm-chitosan is N; the O-cm-chitosan (N, O-CMC) or the N-ethanoyl, O-cm-chitosan or O-cm-chitosan; its molecular structure is as follows
Wherein the substituting group on the N is chosen a kind of in kharophen, carboxymethylamino, amino; Contain cm-chitosan 1～5g in every 100ml carboxymethyl chitosan sugar aqueous solution, chitosan powder or chitin powder 0.5～2g, glycerine 1～5g.
2. the carboxymerhyl chitosan sponge with water-swelling property according to claim 1 is characterized in that: its shape can be any in sheet, bulk, strip, the column.
3. the carboxymerhyl chitosan sponge with water-swelling property according to claim 1 is characterized in that: described environment-friendly type ion crosslinking agent is to choose any one kind of them in water-soluble aluminum salt, calcium salt, the molysite, and concentration is 1～20%.
4. one kind by the described preparation method with carboxymerhyl chitosan sponge of water-swelling property of claim 1, adopt the carboxymethyl chitosan sugar aqueous solution to make, the aqueous solution comprises cm-chitosan, chitosan powder or chitin powder, glycerol plasticizer and environment-friendly type ion crosslinking agent, it is characterized in that: make in every 100ml solution to contain cm-chitosan 1～5g, chitosan powder or chitin powder 0.5～2g, glycerine 1～5g, mix under 50 ℃, it is full cross-linked that the foaming back adds the environment-friendly type ion crosslinking agent under the room temperature, after-20 ℃ of abundant freezing shapings, lyophilize 24 hours.
5. the purposes of the described carboxymerhyl chitosan sponge of claim 1 is characterized in that: the medical field that is used for surgical hemostasis, cavity hemostasis, wound healing.
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| CNB2005100245033A CN100341933C (en) | 2005-03-21 | 2005-03-21 | Carboxymerhyl chitosan sponge with water-absorbent dilatability and its preparation method and use thereof |
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| CN100341933C true CN100341933C (en) | 2007-10-10 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348272C (en) * | 2006-06-23 | 2007-11-14 | 华南理工大学 | Method for preparing astringent sponge of soluble cellulose |
| CN100443123C (en) * | 2006-07-14 | 2008-12-17 | 青岛博益特生物材料有限公司 | Medical chitosan dressing and its application |
| CN101654537B (en) * | 2009-09-04 | 2011-03-02 | 宋炜 | Carboxymethyl chitosan/polyvinyl alcohol compound sponge and preparation method thereof |
| CN101927027A (en) * | 2010-04-16 | 2010-12-29 | 哈尔滨工业大学 | Chitosan/carboxymethyl chitosan rapid hemostatic sponge and preparation method thereof |
| CN102321277B (en) * | 2011-07-12 | 2013-04-24 | 杭州电子科技大学 | Ionic crosslinked chitosan organic acid salt and Carboxymethyl chitosan or sulfated chitosan or sulfated carboxymethyl chitosan electrolyte composite film and preparation method thereof |
| CN102416194A (en) * | 2011-11-11 | 2012-04-18 | 汤小国 | Novel chitosan hemostatic sponge and preparation method thereof |
| CN102813957A (en) * | 2012-09-14 | 2012-12-12 | 上海白衣缘生物工程有限公司 | Biological membrane which promotes healing and preparation method thereof |
| CN106511370A (en) * | 2016-11-02 | 2017-03-22 | 上海陶盛生物技术有限公司 | Bacteriostatic liquid |
| CN108047467B (en) * | 2017-12-12 | 2020-12-18 | 暨南大学 | Medical chitosan carboxymethyl chitosan cross-linked sponge and preparation method thereof |
| CN109331217A (en) * | 2018-12-05 | 2019-02-15 | 元化科技（嘉兴）有限公司 | Styptic sponge and its preparation process |
| CN111202867B (en) * | 2020-03-05 | 2022-04-22 | 山东陆海蓝圣生物科技股份有限公司 | High-water-absorption and water-resistance double-layer composite hemostatic sponge and preparation method thereof |
| CN114366816B (en) * | 2022-01-05 | 2023-06-20 | 重庆福美干细胞生物科技发展有限公司 | Chitosan nanoparticle with excellent freeze-drying redispersibility, freeze-drying preparation, and preparation method and application thereof |
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| WO1998040414A1 (en) * | 1997-02-25 | 1998-09-17 | Linde Ag | A continuous process for effecting gas liquid reactions |
| CN1406632A (en) * | 2001-09-10 | 2003-04-02 | 中国人民解放军军事医学科学院卫生装备研究所 | Collagen based composite sponge and production thereof |
| CN1485097A (en) * | 2003-08-22 | 2004-03-31 | 北京益而康生物工程开发中心 | Prepration process for biologic hemostatic sponge material |
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Patent Citations (4)
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|---|---|---|---|---|
| CN1097980A (en) * | 1993-07-28 | 1995-02-01 | 湛江市卫生材料厂 | Chitosan gelatin sponge |
| WO1998040414A1 (en) * | 1997-02-25 | 1998-09-17 | Linde Ag | A continuous process for effecting gas liquid reactions |
| CN1406632A (en) * | 2001-09-10 | 2003-04-02 | 中国人民解放军军事医学科学院卫生装备研究所 | Collagen based composite sponge and production thereof |
| CN1485097A (en) * | 2003-08-22 | 2004-03-31 | 北京益而康生物工程开发中心 | Prepration process for biologic hemostatic sponge material |
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