CN104436280B - Composite material of potato starch system for stopping bleeding and preventing adhesion and preparation method thereof - Google Patents
Composite material of potato starch system for stopping bleeding and preventing adhesion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite material of a potato starch system for stopping bleeding and preventing adhesion and a preparation method thereof. The composite material comprises anti-adhesion fiber yarns which are mutually interweaved and are prepared from organic polymers with weight-average molecular weight of 50,000-500,000, and hemostatic powder which is attached to the outer surfaces of the anti-adhesion fiber yarns and is prepared from potato starch with a crosslinking degree of 25-50 percent. According to the composite material, the hemostatic powder of potato starch is attached to the outer surfaces of the anti-adhesion fiber yarns which are mutually interweaved, can quickly form gel to adhere to a wound surface, and can be diluted and adsorbed after being completely gelatinized, so that the hemostatic effect is good, the hemostatic speed is high, wound healing is not influenced, and adhesion occurring after an operation can be effectively reduced. Furthermore, coagulation is locked in a fiber membrane prepared from mutually interweaved anti-adhesion fiber yarns, and thus the wound is further protected.
Description
Technical field
The present invention relates to the technical field of bio-medical material, more particularly, to a kind of bleeding stopping and adherence preventing of potato starch system
Composite and preparation method thereof.
Background technology
Peritoneum sustains damage, rubs, burning, be dried and abnormal contact, infection after, the permeability of blood vessel increases, through histamine
Mediation produces inflammatory exudate and fibrin matrix, and fibrin matrix can be gone by internal fibrinolysiss process
Remove.Under normal circumstances, Fibrinolytic Activities are activated, fibrinolysiss, peritoneal mesothelium.But the office leading to because of operation wound
Under the abnormal conditions such as portion's ischemia, Fibrinolytic Activities are suppressed, and fibrin forms bridging, ultimately forms adhesion.Post operation
Adhesion is domestic and international surgical field one of still unsolved important difficult medical problem so far.Adhesion not only can cause serious
Complication, and bad adhesion is also the one of the main reasons that during operation again, complication substantially increases.Preferably anti material
Material should have low irritability, suitable tissue adherence；Wound surface can be completely covered and have enough when retaining in vivo
Between；Can degraded and absorbed be drawn off without second operation；Wound healing；There is certain mechanical strength simultaneously and be easy to
Implement operation etc..Existing listed adherence preventing material, especially membrane material although preventing adhesiving effect is definite, but have clearly
Contraindication, that is, infected wound and active hemorrhage wound disabling.Inflammation and bleeding all can lead to general anti material
Material lost efficacy, especially in art cannot process completely oozing of blood, or remain the wound of a large amount of blood clotting substance after quick-acting haemostatic powder and all can
Wound healing is brought with great negative effect, and the inherently individual complex process of wound healing, the therefore guarantor to wound surface
Shield will consider many factors, if hemostasis and postoperative wound protection effectively can be combined, could be to more preferable
Reduce the harm that oozing of blood and adhesion cause.
Therefore, we urgently find a kind of suitable composite high-molecular material preparation anti-adhesion fiber membrane at present, prepared
Material there is suitable mechanical strength, can realize efficiently treating with bleeding stopping and adherence preventing simultaneously, reach hemostasis, prevention of postoperative viscous
Effect even.The research of our early stages shows can effectively stop postoperative active hemorrhage by compound to hemorrhage and adherence preventing material
Generation, but the selection for hemorrhage consumption, how to be preferably directed to anti after the completion of different wound surface releases and hemostasis
The metabolic problems remaining hemorrhage in film never have solution.Hemostasis gel is also used in combination by we with adherence preventing material simultaneously
Play its each effect, that is, retain the mechanical strength of adherence preventing material and the hemostatic function of hemostasis gel, blood coagulation is locked in material
Do not lure into fibroblast adhesion in material into, do not affect mesothelial cell's healing, because spongy body absorbability is limited, so simultaneously
Compound be suitable only for the little oozing of blood situation of amount of bleeding, more fuzzy for the wound surface visual field, the unconspicuous wound surface in petechia protects
Reason DeGrain.
Existing research shows, powdery hemostatic material has more preferable water absorption than gel and spongiform hemostatic material,
Faster haemostatic effect, however, as zeolites styptic powder quick-acting haemostatic powder process can cause the local temperature of wound too high, starch and
Although polysaccharide styptic powder greatly reduces the exothermic phenomenon of course of dissolution, it is wayward to there is also spraying range, creates after hemostasis
The problems such as face cleaning is difficult, stops blooding particularly with internal, excessive styptic powder may induce excessive inflammatory reaction.Prior art
In hemostatic material be all single use, be difficult to be applied in combination with other membrane materials or gel rubber material realization, typically all
Styptic powder covers Wound protection material again it is impossible to avoid the drawbacks of be used alone after spraying.
Content of the invention
In view of this, one aspect of the present invention provides a kind of composite of the bleeding stopping and adherence preventing of potato starch system, and this is multiple
Condensation material has the hemostasis speed compared with block, simultaneously higher to Wound protection power.
A kind of composite of the bleeding stopping and adherence preventing of potato starch system, comprise by being interweaved and by weight average molecular weight be
The anti cellosilk that 5～500,000 organic polymer is made and be attached to described anti cellosilk appearance and by the degree of cross linking be
The hemostasis powder body that 25～50% potato starch is made.
Anti cellosilk is interweaved and can form fibrous membrane, and hemostasis powder body is scattered in this fibrous membrane.So can make
The blood coagulation that hemostasis powder body produces in hemostasis is locked in fibrous membrane, protects wound further.
Wherein, described organic polymer is selected from Poly(D,L-lactide-co-glycolide, polylactic acid, polylactic acid-glycollic acid copolymerization
Thing, polycaprolactone-one of co-glycolic acid and polycaprolactone or at least two.
A kind of method preparing above-mentioned composite, comprises the following steps：
(1) organic polymer is scattered in organic solvent, obtains macromolecule mixed solution；
(2) potato starch is dispersed in water and obtains suspension, be subsequently added into emulsifying agent and carry out emulsifying, pH to be regulated
Afterwards, add epoxychloropropane to make potato starch crosslink reaction, the product of cross-linking reaction is scattered in organic solvent, obtains
Potato starch suspension；
(3) described macromolecule mixed solution is passed through electrostatic spinning, obtain anti cellosilk；
(4) described potato starch suspension passes through electrostatic spinning, obtains the powder body that stops blooding；
(5) described anti cellosilk and hemostasis powder body are passed through electrostatic spinning, obtain complex fiber material；
(6) described complex fiber material is dried, then thermocompression forming.
Wherein, organic solvent described in step (1) is selected from one of DMF, acetone, THF and hexafluoroisopropanol or at least
Two kinds；
The mass-volume concentration of macromolecule mixed solution is 20～50%.
Emulsifying agent is liquid paraffin and Span 80；
Preferably, the mass ratio of water, liquid paraffin and Span 80 is 10：1～100：1；
Preferably, the 15～80% of suspension quality concentration；
Preferably, pH is 8～11；
Preferably, the ethanol solution of the polyhydric alcohol of described organic solvent mass concentration 3～50%,.
Wherein, the voltage of electrostatic spinning described in step (3) be 10～30KV, solution flow rate be 1～5ml/h, receive away from
From for 5～25cm.
Wherein, the voltage of electrostatic spinning described in step (4) be 10～30KV, solution flow rate be 1～5ml/h, receive away from
From for 5～25cm.
Wherein, the voltage of described electrostatic spinning described in step (5) is 10～30KV, and solution flow rate is 1～5ml/h, connects
Receipts distance is 5～25cm, and the time is 20～180min.
Wherein, drying mode described in step (6) is vacuum drying 24～48 hours；
Preferably, the temperature of described pressure sizing is 45～55 DEG C, and the time is 15～25min.
The hemostasis powder body of potato starch is attached to outside the anti cellosilk being interweaved by the composite of the present invention,
Wound surface can be adhered to by rapid-result gel soon, be diluted adsorbing after complete gelation, haemostatic effect is more excellent, speed of stopping blooding
Hurry up, have no effect on wound healing, can effectively reduce the generation of tissue adhesion.Additionally, blood coagulation is locked by anti cellosilk
In the fibrous membrane being interweaved, protect wound further.
Specific embodiment
To further illustrate technical scheme with reference to embodiment.
Embodiment 1
Macromolecule is dissolved in the organic solvent being made up of DMF, acetone, THF and hexafluoroisopropanol, is configured to quality volume
Concentration is 20% macromolecule mixed solution, is stirred at room temperature 5 hours, obtains macromolecule mixed solution
5g potato starch becomes mass concentration after adding water be 15% suspension, then adds liquid paraffin and Span 80 to enter
Row emulsifying, and the mass ratio of water, liquid paraffin and Span 80 three is 10：1：1, pH maintains 8, adds epoxychloropropane crosslinked
After take out, with ethyl acetate and dehydrated alcohol extracting, hereafter ultrasonic disperse in the polyhydric alcohol/alcohol mixeding liquid in (mass concentration
For 3%), it is configured to suspension stand-by.
It is injected separately into above-mentioned organic polymer mixed solution in 5～8 10ml syringes, add No. 5 rustless steel medicated pillows
(diameter 1～5mm), is 10KV in voltage, and solution flow rate is 1ml/h, and receiving range carries out many shower nozzles electrostatic under conditions of 5cm
Spinning, obtains anti cellosilk.
It is injected separately into above-mentioned potato starch suspension in 3～4 10ml syringes, add that No. 5 rustless steel medicated pillows are (straight
Footpath 1～5mm), it is 10KV in voltage, solution flow rate is 1ml/h, receiving range carries out many shower nozzles Static Spinning under conditions of 5cm
Silk, obtains the powder body that stops blooding.
The shower nozzle that will be equipped with hemostasis powder body is spaced apart with equipped with the filametntary spinning head of anti, is 30KV in voltage,
Solution flow rate is 1ml/h, and receiving range is skill electrostatic spinning 20min under conditions of 5cm, obtains complex fiber material room temperature in vacuo
It is dried 48 hours, remove residual solvent；Heating platen thermocompression forming 25min at a temperature of 45 DEG C；Cut sterilizing can use.
Embodiment 2
Macromolecule is dissolved in the organic solvent being made up of DMF, acetone, THF and hexafluoroisopropanol, is configured to quality volume
Concentration is 50% macromolecule mixed solution, is stirred at room temperature 24 hours, obtains macromolecule mixed solution
The preparation of potato starch suspension：5g potato starch becomes mass concentration after adding water be 80% suspension, then
Add liquid paraffin and Span 80 to carry out emulsifying, and the mass ratio of water, liquid paraffin and Span 80 three is 10：100：1, pH dimension
Hold 11, take out after adding epoxychloropropane crosslinking, with ethyl acetate and dehydrated alcohol extracting, hereafter ultrasonic disperse is in polyhydric alcohol
In/alcohol mixeding liquid in (mass concentration 50%), be configured to suspension stand-by.
It is injected separately into above-mentioned organic polymer mixed solution in 5～8 10ml syringes, add No. 5 rustless steel medicated pillows
(diameter 1～5mm), is 30KV in voltage, and solution flow rate is 5ml/h, and receiving range is quiet for carrying out many shower nozzles under conditions of 25cm
Electrospun, obtains anti cellosilk.
It is injected separately into above-mentioned potato starch suspension in 3～4 10ml syringes, add that No. 5 rustless steel medicated pillows are (straight
Footpath 1～5mm), it is 30KV in voltage, solution flow rate is 5ml/h, receiving range carries out many shower nozzles Static Spinning under conditions of 25cm
Silk, obtains the powder body that stops blooding.
The shower nozzle that will be equipped with hemostasis powder body is spaced apart with equipped with the filametntary spinning head of anti, is 10KV in voltage,
Solution flow rate is 5ml/h, and receiving range is electrostatic spinning 180min under conditions of 25cm, obtains complex fiber material room temperature in vacuo
It is dried 24 hours, remove residual solvent；Heating platen thermocompression forming 15min at a temperature of 55 DEG C；Cut sterilizing can use.
Embodiment 3
Macromolecule is dissolved in the organic solvent being made up of DMF, acetone, THF and hexafluoroisopropanol, is configured to quality volume
Concentration is 35% macromolecule mixed solution, is stirred at room temperature 12 hours, obtains macromolecule mixed solution
The preparation of potato starch suspension：5g potato starch becomes mass concentration after adding water be 48% suspension, then
Add liquid paraffin and Span 80 to carry out emulsifying, and the mass ratio of water, liquid paraffin and Span 80 three is 10：50：1, pH dimension
Hold 9.5, take out after adding epoxychloropropane crosslinking, with ethyl acetate and dehydrated alcohol extracting, hereafter ultrasonic disperse is in polynary
In alcohol/alcohol mixeding liquid in (mass concentration 27%), be configured to suspension stand-by.
It is injected separately into above-mentioned organic polymer mixed solution in 5～8 10ml syringes, add No. 5 rustless steel medicated pillows
(diameter 1～5mm), is 20KV in voltage, and solution flow rate is 3ml/h, and receiving range is quiet for carrying out many shower nozzles under conditions of 15cm
Electrospun, obtains anti cellosilk.
It is injected separately into above-mentioned potato starch suspension in 3～4 10ml syringes, add that No. 5 rustless steel medicated pillows are (straight
Footpath 1～5mm), it is 20KV in voltage, solution flow rate is 3ml/h, receiving range carries out many shower nozzles Static Spinning under conditions of 15cm
Silk, obtains the powder body that stops blooding.
The shower nozzle that will be equipped with hemostasis powder body is spaced apart with equipped with the filametntary spinning head of anti, is 20KV in voltage,
Solution flow rate is 3ml/h, and receiving range is electrostatic spinning 100min under conditions of 5～25cm, obtains complex fiber material room temperature
Vacuum drying 36 hours, removes residual solvent；Heating platen thermocompression forming 20min at a temperature of 50 DEG C；Cut sterilizing can use.
Embodiment 4
Macromolecule is dissolved in the organic solvent being made up of DMF, acetone, THF and hexafluoroisopropanol, is configured to quality volume
Concentration is 30% macromolecule mixed solution, is stirred at room temperature 8 hours, obtains macromolecule mixed solution
The preparation of potato starch suspension：5g potato starch becomes mass concentration after adding water be 30% suspension, then
Add liquid paraffin and Span 80 to carry out emulsifying, and the mass ratio of water, liquid paraffin and Span 80 three is 10：35：1, pH dimension
Hold 8～11, take out after adding epoxychloropropane crosslinking, with ethyl acetate and dehydrated alcohol extracting, hereafter ultrasonic disperse is in many
In first alcohol/alcohol mixeding liquid in (mass concentration 18%), be configured to suspension stand-by.
It is injected separately into above-mentioned organic polymer mixed solution in 5～8 10ml syringes, add No. 5 rustless steel medicated pillows
(diameter 1～5mm), is 15KV in voltage, and solution flow rate is 2.5ml/h, and receiving range carries out many shower nozzles under conditions of 10cm
Electrostatic spinning, obtains anti cellosilk.
It is injected separately into above-mentioned potato starch suspension in 3～4 10ml syringes, add that No. 5 rustless steel medicated pillows are (straight
Footpath 1～5mm), it is 15KV in voltage, solution flow rate is 2.5ml/h, receiving range carries out many shower nozzles electrostatic under conditions of 10cm
Spinning, obtains the powder body that stops blooding.
The shower nozzle that will be equipped with hemostasis powder body is spaced apart with equipped with the filametntary spinning head of anti, is 15KV in voltage,
Solution flow rate is 2.5ml/h, and receiving range is electrostatic spinning 60min under conditions of 10cm, obtains complex fiber material room temperature true
Empty dry 30 hours, remove residual solvent；Heating platen thermocompression forming 18min at a temperature of 50 DEG C；Cut sterilizing can use.
Embodiment 5
Macromolecule is dissolved in the organic solvent being made up of DMF, acetone, THF and hexafluoroisopropanol, is configured to quality volume
Concentration is 35% macromolecule mixed solution, is stirred at room temperature 15 hours, obtains macromolecule mixed solution
The preparation of potato starch suspension：5g potato starch becomes mass concentration after adding water be 45% suspension, then
Add liquid paraffin and Span 80 to carry out emulsifying, and the mass ratio of water, liquid paraffin and Span 80 three is 10：55：1, pH dimension
Hold 10, take out after adding epoxychloropropane crosslinking, with ethyl acetate and dehydrated alcohol extracting, hereafter ultrasonic disperse is in polyhydric alcohol
In/alcohol mixeding liquid in (mass concentration 25%), be configured to suspension stand-by.
It is injected separately into above-mentioned organic polymer mixed solution in 5～8 10ml syringes, add No. 5 rustless steel medicated pillows
(diameter 1～5mm), is 20KV in voltage, and solution flow rate is 3ml/h, and receiving range is quiet for carrying out many shower nozzles under conditions of 15cm
Electrospun, obtains anti cellosilk.
It is injected separately into above-mentioned potato starch suspension in 3～4 10ml syringes, add that No. 5 rustless steel medicated pillows are (straight
Footpath 1～5mm), it is 20KV in voltage, solution flow rate is 3ml/h, receiving range carries out many shower nozzles Static Spinning under conditions of 15cm
Silk, obtains the powder body that stops blooding.
The shower nozzle that will be equipped with hemostasis powder body is spaced apart with equipped with the filametntary spinning head of anti, is 20KV in voltage,
Solution flow rate is 3ml/h, and receiving range is electrostatic spinning 100min under conditions of 15cm, obtains complex fiber material room temperature in vacuo
It is dried 36 hours, remove residual solvent；Heating platen thermocompression forming 20min at a temperature of 50 DEG C；Cut sterilizing can use.
Effectively styptic powder is combined with existing Antiadhesive film in the present invention, retain both respective advantages, be this
Bright key.Absorption styptic anti biomaterial good biocompatibility, granule surface area is big, and rate of water absorption significantly improves,
Substantially reduce bleeding stopping period, effective with fiber film material combines so that blood coagulation is locked in fibrous membrane, protects further
Wound.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (13)
1. a kind of preparation method of potato starch system bleeding stopping and adherence preventing composite is it is characterised in that comprise the following steps：
(1) organic polymer is scattered in organic solvent, obtains macromolecule mixed solution；
Described organic macromolecule weight average molecular weight is 5～500,000, and described organic polymer is selected from poly lactic-co-glycolic acid copolymerization
Thing, polylactic acid, polylactic-co-glycolic acid, polycaprolactone-one of co-glycolic acid and polycaprolactone or at least
Two kinds；
(2) potato starch is dispersed in water and obtains suspension, be subsequently added into emulsifying agent and carry out emulsifying, after pH to be regulated, plus
Entering epoxychloropropane makes potato starch crosslink reaction, the product of cross-linking reaction is scattered in organic solvent, obtains Rhizoma Solani tuber osi
Starch suspension；
(3) described macromolecule mixed solution is passed through electrostatic spinning, obtain anti cellosilk；
(4) described potato starch suspension passes through electrostatic spinning, obtains the powder body that stops blooding；
(5) described anti cellosilk and hemostasis powder body are passed through electrostatic spinning, obtain complex fiber material；
(6) described complex fiber material is dried, then thermocompression forming.
2. preparation method according to claim 1 it is characterised in that organic solvent described in step (1) be selected from DMF, third
One of ketone, THF and hexafluoroisopropanol or at least two.
3. preparation method according to claim 1 is it is characterised in that the matter of macromolecule mixed solution described in step (1)
Amount volumetric concentration is 20～50%.
4. preparation method according to claim 1 it is characterised in that emulsifying agent described in step (2) be liquid paraffin and
Span 80.
5. preparation method according to claim 4 is it is characterised in that the mass ratio of water, liquid paraffin and Span 80 is 10：
1～100：1.
6. preparation method according to claim 1 it is characterised in that suspension quality concentration 15～80%.
7. preparation method according to claim 1 is it is characterised in that pH is 8～11.
8. preparation method according to claim 1 it is characterised in that in described step (2) organic solvent be mass concentration 3
The ethanol solution of～50% polyhydric alcohol.
9. preparation method according to claim 1 is it is characterised in that the voltage of electrostatic spinning described in step (3) is 10
～30KV, solution flow rate is 1～5ml/h, and receiving range is 5～25cm.
10. preparation method according to claim 1 is it is characterised in that the voltage of electrostatic spinning described in step (4) is 10
～30KV, solution flow rate is 1～5ml/h, and receiving range is 5～25cm.
11. preparation methoies according to claim 1 are it is characterised in that the voltage of described electrostatic spinning described in step (5)
For 10～30KV, solution flow rate is 1～5ml/h, and receiving range is 5～25cm, and the time is 20～180min.
12. preparation methoies according to claim 1 are it is characterised in that drying mode described in step (6) is vacuum drying
24～48 hours.
13. preparation methoies according to claim 1 it is characterised in that described thermocompression forming temperature be 45～55 DEG C, when
Between be 15～25min.
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| CN201410637196.5A CN104436280B (en) | 2014-11-12 | 2014-11-12 | Composite material of potato starch system for stopping bleeding and preventing adhesion and preparation method thereof |
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| KR20010074825A (en) * | 1998-08-14 | 2001-08-09 | 야스히꼬 시미즈 | Topically Absorbent Hemostatic Material |
| GB2461019B (en) * | 2008-04-25 | 2013-06-05 | Medtrade Products Ltd | Haemostatic material |
| CN103418024A (en) * | 2012-05-18 | 2013-12-04 | 无锡圆容生物医药股份有限公司 | Novel absorbent medical material |
| CN102921050A (en) * | 2012-11-09 | 2013-02-13 | 无锡中科光远生物材料有限公司 | Preparation method of anti-adhesion fibrous membrane with hemostatic function |
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