CN109381730A

CN109381730A - The preparation method and PVA-CS-SA spinning fibre film of PVA-CS-SA spinning fibre film and application

Info

Publication number: CN109381730A
Application number: CN201811438167.0A
Authority: CN
Inventors: 于晖; 陈君娴; 蒋瑞璇; 蔡洁; 李英毅; 朱吉昌; 曾健豪; 郭永诗; 黄琪帏; 邹捷
Original assignee: Wuyi University
Current assignee: Wuyi University
Priority date: 2018-11-27
Filing date: 2018-11-27
Publication date: 2019-02-26

Abstract

The present invention provides a kind of preparation method of PVA-CS-SA spinning fibre film and PVA-CS-SA spinning fibre film and applications, are related to field of medical article technology.The preparation method of PVA-CS-SA spinning fibre film, include the following steps: that PVA and CS blend spinning liquid and PVA and CS blend spinning liquid are obtained the first PVA-CS spinning film, PVA-SA spinning film and the 2nd PVA-CS spinning film through electrostatic spinning by (a), obtains composite membrane；(b) by composite membrane successively crosslinked reaction and complex reaction, PVA-CS-SA spinning fibre film is obtained.The spinning fibre film functional diversities that the present invention obtains, while having high-hygroscopicity, hemostatic and biocidal property function concurrently, it can satisfy the physiological environment requirement of wound healing complexity.

Description

The preparation method and PVA-CS-SA spinning fibre film of PVA-CS-SA spinning fibre film and Using

Technical field

The present invention relates to field of medical article technology, more particularly, to a kind of preparation side of PVA-CS-SA spinning fibre film Method and PVA-CS-SA spinning fibre film and application.

Background technique

With the development of society, the problem of world population ages becomes increasingly conspicuous, the health problem of the elderly causes height The concern of degree, Cutaneous disease are even more by greatest concern, and since old human metabolism is slack-off, cell growth is slack-off, Wound infection, if the chronic wound cares such as suppuration cannot treat well will generate secondary injury.With medical level Be gradually increased, the demand of high-end casting product steeply rises, and then has attracted a large amount of curable product import, but price ratio Costly.And conventional medical dressing presence has a single function or multiple functions can not act synergistically, and lacks combination therapy function, nothing Method meets the physiological environment requirement of wound healing complexity.Therefore, it is necessary to develop multifunctional bio-active type medical dressing, make dressing Develop from simple function to multifunction, is the application requirement and development trend of medical dressing now.

In view of this, the present invention is specifically proposed.

Summary of the invention

The first object of the present invention is to provide a kind of preparation method of PVA-CS-SA spinning fibre film, existing to alleviate The spinning fibre film that existing preparation method present in technology obtains has a single function, and lacks combination therapy function, is unable to satisfy The technical problems such as the physiological environment requirement of wound healing complexity.

The preparation method of PVA-CS-SA spinning fibre film provided by the invention, includes the following steps:

(a) PVA and CS blend spinning liquid is obtained into the first PVA-CS spinning film through electrostatic spinning；Then PVA and SA are mixed It closes spinning solution and obtains PVA-SA spinning film through electrostatic spinning, be superimposed upon PVA-SA spinning film on the first PVA-CS spinning film； PVA and CS blend spinning liquid is obtained into the 2nd PVA-CS spinning film through electrostatic spinning again, is superimposed upon the 2nd PVA-CS spinning film On PVA-SA spinning film, composite membrane is obtained；

(b) by composite membrane successively crosslinked reaction and complex reaction, PVA-CS-SA spinning fibre film is obtained.

Further, the concentration of the PVA and CS blend spinning liquid be 7-9wt%, preferably 8-9wt%, further it is excellent It is selected as 9wt%；

And/or the concentration of the PVA and SA blend spinning liquid be 6-9wt%, preferably 6-8wt%, further preferably 7.2wt%.

Further, the mass ratio of PVA and CS is (3-5): 1, preferably (4-5) in PVA the and CS blend spinning liquid: 1, further preferably 4:1；

And/or the mass ratio of PVA and SA is (10-70): (3-10) in PVA the and SA blend spinning liquid, preferably (50-70): (6-10), further preferably 50:10.

Further, in the step (b), composite membrane is first reacted with cross-linking agents, then with complexing agent complex reaction, Obtain PVA-CS-SA spinning fibre film；

The crosslinking agent includes dialdehyde or acid anhydrides, preferably dialdehyde, further preferably glutaraldehyde, malonaldehyde or butanedial At least one of, it is still more preferably glutaraldehyde；

The complexing agent includes soluble calcium salt, preferably at least one of calcium chloride, calcium sulfate or calcium nitrate, into one Step is preferably calcium chloride.

Further, in the step (b), composite membrane is first reacted with the aqueous solution vapor crosslinking of glutaraldehyde, then with chlorine The alcoholic solution complex reaction for changing calcium, obtains PVA-CS-SA spinning fibre film；

Preferably, the concentration of the aqueous solution of the glutaraldehyde is 45-55wt%, preferably 50-55wt%；And/or crosslinking Time is 20-25h, preferably 20-24h；

Preferably, the concentration of the alcoholic solution of the calcium chloride is 2-4wt%, preferably 3-4wt%；And/or crosslinking time For 1-3h, preferably 1.5-3h.

Further, in the step (a), the spinning condition of the PVA and CS blend spinning liquid are as follows: spinning voltage is 15-20kv, preferably 16-20kv；

And/or rate of flooding 0.3-1mL/h, preferably 0.8-1mL/h；

And/or spinning distance is 10-12cm, preferably 11-12cm；

And/or spinning humidity is 40-50%, preferably 45-50%.

Further, in the step (a), the spinning condition of the PVA and SA blend spinning liquid are as follows: spinning voltage is 15-20kv, preferably 16-20kv；

And/or rate of flooding 0.3-0.5mL/h, preferably 0.4-0.5mL/h；

And/or spinning distance is 10-12cm, preferably 11-12cm；

And/or spinning humidity is 40-50%, preferably 45-50%.

Further, the preparation method of the PVA and CS blend spinning liquid includes the following steps:

(l) PVA solution is obtained by PVA is soluble in water；

(m) CS is dissolved in acetic acid solution and obtains CS solution；

(n) PVA solution and CS solution are mixed to get PVA and CS blend spinning liquid；

And/or the preparation method of the PVA and SA blend spinning liquid includes the following steps:

(o) PVA solution is obtained by PVA is soluble in water；

(p) SA solution is obtained by SA is soluble in water；

(q) PVA solution and SA solution are mixed to get PVA and SA blend spinning liquid；

Preferably, in the step (l), the concentration of the PVA solution is 15-25wt%, preferably 15-20wt%；

Preferably, in the step (m), the concentration of the CS solution is 1-5wt%, preferably 1-3wt%；

Preferably, in the step (o), the concentration of the PVA solution is 10-20wt%, preferably 10-15wt%；

Preferably, in the step (p), the concentration of the SA solution is 1-5wt%, preferably 1-3wt%.

The second object of the present invention is to provide a kind of PVA-CS-SA spinning fibre film, functional diversities, while having height concurrently Hygroscopicity, hemostatic and biocidal property function can satisfy the physiological environment requirement of wound healing complexity, can by ion exchange Reach hemostasia effect, reduces pain, prevent the infection and growth of bacterium.

PVA-CS-SA spinning fibre film provided by the invention, is prepared by above-mentioned preparation method.

The third object of the present invention is to provide a kind of PVA-CS-SA spinning fibre film that above-mentioned preparation method is prepared Or above-mentioned PVA-CS-SA spinning fibre film is preparing the application in medical dressing, by PVA-CS-SA spinning fibre film preparation at doctor It with dressing, functional diversities, while having high-hygroscopicity, hemostatic and biocidal property function concurrently, wound is made to be in moderately wet In environment, promote growth factor release, stimulate cellular proliferation, power of regeneration and the cell for improving epidermal cell are mobile, promote wound Wound healing time is shortened in mouth healing, and a piece of dressing can not be needed to replace, be reduced always using up to wound recovery from illness Medical dressing dosage.

Compared with prior art, the invention has the following advantages:

The preparation method of PVA-CS-SA spinning fibre film provided by the invention is with polyvinyl alcohol, chitosan and sodium alginate For raw material, polyvinyl alcohol has good biocompatibility, has outstanding aqueous gel performance, is a kind of safe film forming Agent；Chitosan has the effects that improve immune and activating cell have very strong hygroscopicity；Sodium alginate has anticoagulant work With, it may have the characteristic for facilitating film forming, by PVA and CS blend spinning liquid and PVA and SA blend spinning liquid respectively through electrostatic spinning, Composite membrane is obtained after superposition, then successively through A class crosslinking agent and B class crosslinking agent it is appropriately crosslinked after to obtain PVA-CS-SA spinning fine Tie up film.The raw material of the preparation method is easy to get, cheap, easy to operate, easily controllable, and obtained spinning fibre film is vdiverse in function Change, while having high-hygroscopicity, hemostatic and biocidal property function concurrently, can satisfy the physiological environment requirement of wound healing complexity, It can reach hemostasia effect by ion exchange, reduce pain, prevent the infection and growth of bacterium.

Spinning fibre film provided by the invention, functional diversities, while having high-hygroscopicity, hemostatic and biocidal property function concurrently Can, it can satisfy the physiological environment requirement of wound healing complexity, can reach hemostasia effect by ion exchange, reduce pain, resistance The only infection and growth of bacterium.

The present invention at medical dressing, functional diversities, while having the film preparation of PVA-CS-SA spinning fibre highly hygroscopic concurrently Property, hemostatic and biocidal property function, be in wound in moderately wet environment, promote growth factor release, stimulate cell Proliferation, power of regeneration and the cell for improving epidermal cell are mobile, promote wound healing, shorten wound healing time, and a piece of Dressing can fully recover using up to wound always, do not need to replace, reduce medical dressing dosage.

Detailed description of the invention

It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, is also possible to obtain other drawings based on these drawings.

Fig. 1 is the structural schematic diagram for the PVA-CS-SA spinning fibre film that the embodiment of the present invention two is prepared；

Fig. 2 is the PVA-CS spinning film and PVA- for the PVA-CS-SA spinning fibre film that the embodiment of the present invention two is prepared The picture that SA spinning film is observed under an optical microscope, Fig. 2 (a) are PVA-CS spinning film, and Fig. 2 (b) is PVA-SA spinning film；

Fig. 3 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that comparative example one is prepared The picture that film is observed under an optical microscope, Fig. 3 (a) are PVA-CS spinning film, and Fig. 3 (b) is PVA-SA spinning film；

Fig. 4 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that comparative example two is prepared The picture that film is observed under an optical microscope, Fig. 4 (a) are PVA-CS spinning film, and Fig. 4 (b) is PVA-SA spinning film；

Fig. 5 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that comparative example three is prepared The picture that film is observed under an optical microscope, Fig. 5 (a) are PVA-CS spinning film, and Fig. 5 (b) is PVA-SA spinning film；

Fig. 6 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that comparative example four is prepared The picture that film is observed under an optical microscope, Fig. 6 (a) are PVA-CS spinning film, and Fig. 6 (b) is PVA-SA spinning film；

Fig. 7 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that comparative example five is prepared The picture that film is observed under an optical microscope, Fig. 7 (a) are PVA-CS spinning film, and Fig. 7 (b) is PVA-SA spinning film；

Fig. 8 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that comparative example six is prepared The picture that film is observed under an optical microscope, Fig. 8 (a) are PVA-CS spinning film, and Fig. 8 (b) is PVA-SA spinning film.

Specific embodiment

Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention. The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument are not Production firm person is indicated, is the conventional products that can be obtained by commercially available purchase.

PVA and SA blend spinning liquid in the present invention refers to the suspension containing PVA and SA, PVA and SA blend spinning The concentration of liquid refers to the sum of the concentration of PVA and SA in blend spinning liquid.

According to the first aspect of the invention, the present invention provides a kind of preparation method of PVA-CS-SA spinning fibre film, Include the following steps:

PVA is the abbreviation of polyvinyl alcohol (polyvinyl alcohol), organic compound, white plates, cotton-shaped or powder Shape solid, it is tasteless, it is dissolved in water, insoluble in organic solvents such as gasoline, kerosene, is slightly soluble in dimethyl sulfoxide, is important chemical industry original Material.Pharmaceutical polyvinyl alcohol is a kind of extremely safe macromolecule organic, and has good biocompatibility, in eye Also apply the characteristic of its aqueous gel in terms of section, wound dressing and joint prosthesis, at the same polyvinyl alcohol film in medicinal film and Organ film etc. also has use, and safety has some idea of from for wound skin repair and eye eye drop product, also often It is used in the facial mask in cosmetics, face cleaning cream, is the film forming agent of safety in toner.

CS is the abbreviation of chitosan (chitosan), using chitin as raw material, through refining, and not soluble in water and alkali soluble Liquid can be dissolved in diluted acid, can be absorbed by the body.Chitosan is the first order derivatives of chitin, the blood phase of this natural polymer The excellent performances such as capacitive, safety and microbic resolvability are prominent, in medical, bioengineering, chemical industry, cosmetics, water process, gold The application study for belonging to the numerous areas such as extraction and recycling achieves major progress.For patient, chitosan has reducing blood lipid and drop The effect of blood glucose.

The discarded shrimp shell of aquatic products processing factory and crab shell are the primary raw materials for preparing chitosan, and main component has calcium carbonate, egg White matter and chitin (20% or so).Wherein shrimp and crab shells are prepared into through the four-stage of decalcification, deproteinized matter, decoloration and desacetoxy To chitosan.

SA is the abbreviation of sodium alginate (Sodium alginate), is had for white or pale yellow powder, odorless, tasteless Very strong hygroscopicity, sodium alginate powder are met water and are got wet, and extremely strong hygroscopicity makes its moisture absorption rear surface have viscosity, then Powdered sodium alginate is adhesively-bonded together to form rapidly agglomerate, and the complete aquation that agglomerate will be slow in water simultaneously dissolves.Seaweed Stability, dissolubility, viscosity and safety needed for sour sodium has pharmaceutical preparation auxiliary material.It has concentrate solution, forms gel With the ability of film forming, it is commonly used for the sizing agent, printing paste and dyeing assistant of textile, while as thickener, stabilizer and cream Agent is widely used in food industry, can be made into film, is used for candy release packaging.Sodium alginate because have anticoagulation, Reducing blood lipid and the effect for reducing blood viscosity, can make the hemostat of various dosage forms, including styptic sponge used, hemostatic gauze, hemostasis Film, scald gauze and spraying hemostat etc.；Also have effects that increase blood volume and maintain blood pressure, before being usually used in stabilization procedure The rear circulatory system is bled profusely, the whole bodies dehydration such as burn shock and acute dysentery etc..

Due to not being blended between PVA solution, CS solution and SA solution, need PVA and CS blend spinning liquid and PVA and SA Blend spinning liquid is separately formulated.

Electrostatic spinning is carried out using electrostatic spinning machine in step (a).

Debugging electrostatic spinning machine: PVA the and CS blend spinning liquid prepared and PVA and SA blend spinning liquid are poured into rule respectively After the identical syringe of lattice, metal needle is put upside down standing upwards, so that bubble in syringe is then squeezed discharge toward rising, reduces Influence to spinning result.After bubble is discharged, syringe is mounted on spinning machine and is fixed.Syringe needle is connected into high-pressure electrostatic again Conducting wire.Syringe needle is passed through using the plastic sheet of insulation and covers spinning machine, prevents the metal part of spinning machine from generating shadow to electrostatic field The phenomenon that ringing and fiber caused to spray backward.Spinning electromechanical source is opened after adjusting the spinning distance of reception device, spinning parameter is set After, " perfusion accelerates " key is pressed, is oozed if any spinning solution from syringe needle, then position is adjusted successfully；As do not oozed, then need after It is continuous to be adjusted.The power supply of reception device is opened, ground wire is connected, adjusting revolving speed is 3.2r/s, and reception device is allowed to run first.It presses " perfusion starts " key of lower spinning machine, and open high-voltage static power adjusts voltage to requiring spinning section.

Electrostatic spinning process: PVA the and CS blend spinning liquid of injection equivalent is total in the syringe of first Xiang Sanzhi same size With work, the first PVA-CS spinning film is first received on the reception device, after reaching certain thickness；Then three same sizes are replaced Syringe, inject PVA the and SA blend spinning liquid of equivalent, continue spinning, continue on the basis of the first PVA-CS spinning film PVA-SA spinning film is received, in the case where sufficiently thick, then the syringe of three same sizes is replaced, injects the PVA and CS of equivalent Blend spinning liquid continues spinning, continues to the 2nd PVA-CS spinning film on the basis of PVA-SA spinning film, superposition constitutes The composite membrane of " sandwich " structure.Can according to the needs of product according to aforesaid operations at least once.

Crosslinking is exactly to connect to reticulate or the process of three-dimensional polymeric molecule with covalent bond between line style or branch type macromolecular chain, high score New connecting key is formed between subchain and generates the reaction of reticular polymer.Complexing is exactly that metal ion and line style or branch type are high Molecule interchain is reticulated with co-ordinate covalent bond connection.Composite membrane is greatly improved spinning fibre film after appropriately crosslinked and complexing Water-resistance, flexibility and intensity etc..

The preparation method of PVA-CS-SA spinning fibre film provided by the invention is with polyvinyl alcohol, chitosan and sodium alginate For raw material, polyvinyl alcohol has good biocompatibility, has outstanding aqueous gel performance, is a kind of safe film forming Agent；Chitosan has the effects that improve immune and activating cell have very strong hygroscopicity；Sodium alginate has anticoagulant work With, it may have the characteristic for facilitating film forming, by PVA and CS blend spinning liquid and PVA and SA blend spinning liquid respectively through electrostatic spinning, Composite membrane is obtained after being sequentially overlapped, then successively crosslinked reaction and complex reaction obtain PVA-CS-SA spinning fibre film.The preparation The raw material of method is easy to get, cheap, easy to operate, easily controllable, and obtained spinning fibre film functional diversities have concurrently simultaneously High-hygroscopicity, hemostatic and biocidal property function can satisfy the physiological environment requirement of wound healing complexity, by ion exchange It can reach hemostasia effect, reduce pain, prevent the infection of bacterium and the purpose of growth.

In a preferred embodiment, the concentration of the PVA and CS blend spinning liquid is 7-9wt%, preferably 8- 9wt%, further preferably 9wt%.

The concentration of PVA and CS blend spinning liquid is the concentration of PVA and CS in the present invention.

The concentration of spinning solution has decisive influence to spinning result, and concentration is too low, cannot be at silk, directly ejection spinning Liquid, string-of-pearls-like are more；Excessive concentration, it may appear that fracture of wire, syringe needle blocking, the diameter of fiber are unstable, it is therefore desirable to which suitable is dense Spinning section is spent, spinning could be started, to be stablized, the fiber of uniform diameter.

Wherein, the concentration of PVA and CS blend spinning liquid for example can be, but be not limited to 7wt%, 7.2wt%, 7.4wt%, 7.6wt%, 7.8wt%, 8wt%, 8.2wt%, 8.4wt%, 8.6wt%, 8.8wt% or 9wt%.

In a preferred embodiment, the concentration of the PVA and SA blend spinning liquid is 6-9wt%, preferably 6- 8wt%, further preferably 7.2wt%.

The concentration of PVA and SA blend spinning liquid is the concentration of PVA and SA in the present invention.

The concentration of spinning solution has decisive influence to spinning result, and concentration is too low, cannot be at silk, directly ejection spinning Liquid, string-of-pearls-like are more；Excessive concentration, it may appear that fracture of wire, syringe needle blocking, the diameter of fiber are unstable, it is therefore desirable to suitable spinning Silk concentration ranges, could start spinning, to be stablized, the fiber of uniform diameter.

Wherein, the concentration of PVA and SA blend spinning liquid for example can be, but be not limited to 6wt%, 6.2wt%, 6.4wt%, 6.6wt%, 6.8wt%, 7wt%, 7.2wt%, 7.4wt%, 7.6wt%, 7.8wt%, 8wt%, 8.2wt%, 8.4wt%, 8.6wt%, 8.8wt% or 9wt%.

In a preferred embodiment, the mass ratio of PVA and CS is (3-5) in PVA the and CS blend spinning liquid: 1, preferably (4-5): 1, further preferably 4:1.

The PVA content the high more is conducive to spinning, and the CS content the high more is unfavorable for spinning, and CS content is higher to will appear a large amount of pearl String-like causes spinning to fail.The mass ratio of PVA and CS in PVA and CS blend spinning liquid is limited to (3-5) by the present invention: 1, it is excellent Be selected as (4-5): 1, further preferably 4:1 not only can guarantee and has been spun to function, but also CS content can be made higher, make spinning fibre film Have the effects that higher immune and activating cell and better hygroscopicity.

In a preferred embodiment, the mass ratio of PVA and SA is (10- in PVA the and SA blend spinning liquid 70): (3-10), preferably (50-70): (6-10), further preferably 50:10.

The PVA content the high more is conducive to spinning, and the SA content the high more is unfavorable for spinning, and SA content is higher to will appear a large amount of pearl String-like, or even spinning solution is directly sprayed, cause the failure of spinning.The present invention is by the matter of PVA and SA in PVA and SA blend spinning liquid Amount ratio is limited to (10-70): (3-10), preferably (50-70): (6-10), further preferably 50:10 both can guarantee spinning Success, and SA content can be made higher, make spinning fibre film that there is better hemostatic function.

Wherein, the mass ratio of PVA and SA such as can be in PVA and SA blend spinning liquid, but be not limited to 10:3,70:10, 70:3,50:10,70:9 or 70:6.

In a preferred embodiment, in the step (b), composite membrane is first reacted with cross-linking agents, then with Complexing agent complex reaction obtains PVA-CS-SA spinning fibre film；

Crosslinking agent includes dialdehyde or acid anhydrides, preferably dialdehyde, further preferably in glutaraldehyde, malonaldehyde or butanedial At least one is still more preferably glutaraldehyde.In crosslinking agent containing there are two aldehyde radical or two carbonyls, can make polyvinyl alcohol, Aldol condensation occurs for the hydroxyl in chitosan and sodium alginate, makes to form new connecting key between macromolecular chain and generate netted knot Structure.Complexing agent includes soluble calcium salt, preferably at least one of calcium chloride, calcium sulfate or calcium nitrate, further preferably Calcium chloride.Calcium ion and sodium alginate in complexing agent are complexed with co-ordinate covalent bond, form cross-linked structure.Composite membrane is successive After reacting with crosslinking agent and complexing agent, water-resistance, flexibility and intensity of spinning fibre film etc. can be improved.

In a preferred embodiment, in the step (b), composite membrane is first handed over the aqueous solution steam of glutaraldehyde Connection reaction, then the alcoholic solution complex reaction with calcium chloride, obtain PVA-CS-SA spinning fibre film.

Concrete operations are as follows: unloading composite membrane on the reception device, clip specification is the sample of 5cm*5cm in the middle part of composite membrane Product；

Smooth foam is placed on to the bottom of air dryer, is placed on ventilation operation platform, and by the water-soluble of glutaraldehyde Liquid slowly pours into glass dish, and glass dish is slowly put into air dryer and is placed on foam, puts rack into, by air Drier puts 37 DEG C of preheating 30min in electric heating convection oven into；

It is placed on workbench from air dryer is taken out in electric drying oven with forced convection, slowly pushes bottle cap until beating completely It opens, glutaraldehyde gas is discharged in workbench in closed workbench；

Sample is gently placed on rack with tweezers, is closed the lid, slight friction ensures that air dryer seals back and forth, 37 DEG C of constant temperature decatizes in electric drying oven with forced convection；

Sample is clipped to clean glass dish with tweezers, wraps up entire glass dish using preservative film, with clean metal needle Preservative film is pierced through, vacuum drying in vacuum drying oven is placed in；

The sample after drying is separated with aluminium-foil paper with tweezers, puts the small beaker for filling the ethanol solution of calcium chloride into It is interior, it impregnates.

Sample is taken out from small beaker with tweezers, is scrubbed 3 times in dehydrated alcohol, then be put into clean small beaker, The rim of a cup of small beaker is closed to pierce through preservative film with clean metal needle, be placed in vacuum oven and take out very with preservative film Sky is dry.

Using the vapor of glutaraldehyde solution, it is easily accessible the inside of the reticular structure of composite membrane, it is anti-to be more advantageous to crosslinking The progress answered.

In a kind of preferred embodiment, the concentration of the aqueous solution of the glutaraldehyde is 45-55wt%, preferably 50-55wt%；And/or crosslinking time 20-25h, preferably 20-24h.

Concentration by limiting the aqueous solution of glutaraldehyde can control the degree being crosslinked, and excessive concentration, crosslinking degree is excessive, Cause the flexibility of spinning fibre film poor, intensity is low；Concentration is too low, and crosslinking degree is too small, leads to the water-resistance of spinning fibre film It is deteriorated.The concentration of the aqueous solution of glutaraldehyde is limited to 40-60wt%, preferably 50-60wt% by the present invention, the spinning after making crosslinking Silk fiber film has good water-resistance, flexibility and intensity etc..

The degree of crosslinking can be controlled by limiting the time being crosslinked, overlong time, crosslinking degree is excessive, causes spinning fine The flexibility for tieing up film is poor, and intensity is low；Time is too short, and crosslinking degree is too small, still has moieties not generate new keys, leads to spinning The water-resistance of tunica fibrosa is deteriorated.Crosslinking time is limited to 20-25h, preferably 20-24h by the present invention, and the spinning after making crosslinking is fine Tieing up film has good water-resistance, flexibility and intensity etc..

Wherein, the concentration of the aqueous solution of glutaraldehyde for example can be, but be not limited to 45wt%, 46wt%, 48wt%, 50wt%, 52wt% or 54wt%, 55wt%；Crosslinking time for example can be, but be not limited to 20h, 21h, 22h, 23h, for 24 hours or 25h。

In a kind of preferred embodiment, the concentration of the alcoholic solution of the calcium chloride is 2-4wt%, preferably 3- 4wt%；And/or crosslinking time 1-3h, preferably 1.5-3h.

Concentration by limiting the alcoholic solution of calcium chloride can control the degree being crosslinked, and excessive concentration, crosslinking degree is excessive, Cause the flexibility of spinning fibre film poor, intensity is low；Concentration is too low, and crosslinking degree is too small, still has moieties not generate newly Key causes the water-resistance of spinning fibre film to be deteriorated.The concentration of the alcoholic solution of calcium chloride is limited to 2-4wt% by the present invention, preferably For 3-4wt%, the spinning fibre film after making crosslinking has good water-resistance, flexibility and intensity etc..

Wherein, the concentration of the alcoholic solution of calcium chloride for example can be, but be not limited to 2wt%, 2.2wt%, 2.4wt%, 2.6wt%, 2.8wt%, 3wt%, 3.2wt%, 3.4wt%, 3.6wt%, 3.8wt% or 4wt%.

In a preferred embodiment, in the step (a), the spinning condition of the PVA and CS blend spinning liquid Are as follows: spinning voltage 15-20kv, preferably 16-20kv；

And/or rate of flooding 0.3-1mL/h, preferably 0.8-1mL/h；

And/or spinning distance is 10-12cm, preferably 11-12cm；

And/or spinning humidity is 40-50%, preferably 45-50%.

Overtension, it may appear that fracture of wire, string-of-pearls-like increase, or even occur directly spraying spinning solution to reception device；Voltage Too low, the not up to minimum voltage of spinning solution spinning requirement fails to form spinneret；When voltage reaches suitable spinning voltage section Afterwards, in the range of spinning solution is able to bear, the diameter of fiber can become smaller with the raising of voltage.

Rate of flooding is too fast, it may appear that a large amount of string-of-pearls-like, fibre diameter are unstable；Rate of flooding is excessively slow, it may appear that disconnected Silk, and spinning efficiency is low.

Spinning solution can be concentrated with the volatilization of solution in air when by metal needle and be solidified into fiber, quiet Under the action of electric field, it is able to receive in the reception device of cathode.When the speed of injection is certain, the diameter of fiber can be with syringe needle Become smaller with increase at a distance from reception device, but pay attention to being in receivable section, spinning distance is too short, and spinning solution is also It is not in time for volatilization concentration；Spinning is apart from too long, then reception device does not receive fiber.

Humidity is excessive, and solvent volatilization is insufficient, influences the aerial form of fiber, and humidity is excessive to being added on syringe needle Voltage there is also greater risk, humidity must can just carry out spinning in suitable range.

Wherein, spinning voltage for example can be, spinning voltage for example can be, but be not limited to 15kv, 16kv, 17kv, 18kv, 19kv or 20kv；Rate of flooding for example can be, but be not limited to 0.3mL/h, 0.4mL/h, 0.5mL/h, 0.6mL/h, 0.7mL/h, 0.8mL/h, 0.9 or 1mL/h；Spinning distance for example can be, but be not limited to 10cm, 11cm or 12cm；Spinning is wet Degree for example can be, but be not limited to 40%, 42%, 44%, 46%, 48% or 50%.

In a preferred embodiment, in the step (a), the spinning condition of the PVA and SA blend spinning liquid Are as follows: spinning voltage 15-20kv, preferably 16-20kv；

And/or rate of flooding 0.3-0.5mL/h, preferably 0.4-0.5mL/h；

And/or spinning distance is 10-12cm, preferably 11-12cm；

And/or spinning humidity is 40-50%, preferably 45-50%.

Wherein, spinning voltage for example can be, spinning voltage for example can be, but be not limited to 15kv, 16kv, 17kv, 18kv, 19kv or 20kv；Rate of flooding for example can be, but be not limited to 0.3mL/h, 0.4mL/h or 0.5mL/h；Spinning distance Such as can be, but be not limited to 10cm, 11cm or 12cm；Spinning humidity for example can be, but be not limited to 40%, 42%, 44%, 46%, 48% or 50%.

In a preferred embodiment, the preparation method of the PVA and CS blend spinning liquid includes the following steps:

(l) PVA solution is obtained by PVA is soluble in water；

(m) CS is dissolved in acetic acid solution and obtains CS solution；

(n) PVA solution and CS solution are mixed to get PVA and CS blend spinning liquid.

In a kind of preferred embodiment, in the step (l), the concentration of the PVA solution is 15-25wt%, Preferably 15-20wt%.

Wherein, the concentration of PVA solution for example can be, but be not limited to 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt% or 25wt%.

In a kind of preferred embodiment, in the step (m), the concentration of the CS solution is 1-5wt%, preferably For 1-3wt%.

Wherein, the concentration of CS solution for example can be, but be not limited to 1wt%, 2wt%, 3wt%, 4wt% or 5wt%.

In a preferred embodiment, the preparation method of the PVA and SA blend spinning liquid includes the following steps:

(o) PVA solution is obtained by PVA is soluble in water；

(p) SA solution is obtained by SA is soluble in water；

(q) PVA solution and SA solution are mixed to get PVA and SA blend spinning liquid.

In a preferred embodiment, in the step (o), the concentration of the PVA solution is 10-20wt%, excellent It is selected as 10-15wt%.

Wherein, the concentration of PVA solution for example can be, but be not limited to 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt%.

In a preferred embodiment, in the step (p), the concentration of the SA solution is 1-5wt%, preferably 1-3wt%.

Wherein, the concentration of SA solution for example can be, but be not limited to 1wt%, 2wt%, 3wt%, 4wt% or 5wt%.

According to the second aspect of the invention, the present invention provides a kind of PVA-CS-SA spinning fibre films, by above-mentioned preparation Method is prepared.

PVA-CS-SA spinning fibre film functional diversities provided by the invention, while having high-hygroscopicity, hemostatic and suppression concurrently The function of bacterium property can satisfy the physiological environment requirement of wound healing complexity, can reach hemostasia effect by ion exchange, reduce Pain prevents the infection and growth of bacterium.

According to the third aspect of the present invention, the present invention provides a kind of PVA-CS- that above-mentioned preparation method is prepared SA spinning fibre film or above-mentioned PVA-CS-SA spinning fibre film are preparing the application in medical dressing.

In order to facilitate the clearer understanding present invention, below in conjunction with embodiment and comparative example to technical side of the invention Case is described further.

Embodiment one

The preparation of 1.PVA and CS blend spinning liquid

(1) 20wt% poly-vinyl alcohol solution: weighing 20g polyvinyl alcohol on an electronic balance, is measured with the graduated cylinder of 100mL 80mL distilled water pours the conical flask of 100mL into jointly, puts rotor into；Conical flask is placed in constant temperature blender with magnetic force, is passed through Rotor stirring and dissolving；After dissolution, stands, completely disappeared to bubble.

(2) 2wt% acetic acid solution: weighing 2g acetic acid on an electronic balance, measures 98mL distilled water with the graduated cylinder of 100mL, The conical flask for pouring 100mL into jointly, puts rotor into；Conical flask is placed in constant temperature blender with magnetic force, is stirred by rotor mixed Conjunction.

(3) 3% chitosan solutions: weighing 3g chitosan on an electronic balance, and it is molten to measure 2% acetic acid with the graduated cylinder of 100mL Liquid 97mL pours the conical flask of 100mL into jointly, puts rotor into；Conical flask is placed in constant temperature blender with magnetic force, rotor is passed through Stirring and dissolving；After dissolution, stands, completely disappeared to bubble.

(4) 20wt% poly-vinyl alcohol solution is weighed respectively and 3% chitosan solution is mixed to get PVA and CS blend spinning Liquid.

The preparation of 2.PVA and SA blend spinning liquid

(1) 10wt% poly-vinyl alcohol solution: weighing 10g polyvinyl alcohol on an electronic balance, is measured with the graduated cylinder of 100mL 90mL distilled water pours the conical flask of 100mL into jointly, puts rotor into；Conical flask is placed in constant temperature blender with magnetic force, is passed through Rotor stirring and dissolving；After dissolution, stands, completely disappeared to bubble.

(2) 3% sodium alginate solns: weighing 3g sodium alginate on an electronic balance, measures distilled water with the graduated cylinder of 100mL 97mL pours the conical flask of 100mL into jointly, puts rotor into；Conical flask is placed in constant temperature blender with magnetic force, is stirred by rotor Mix dissolution；After dissolution, stands, completely disappeared to bubble.

(3) it measures 10wt% poly-vinyl alcohol solution respectively and 3% chitosan solution is mixed to get PVA and CS blend spinning Liquid.

Embodiment two

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, includes the following steps:

(1) PVA the and CS blend spinning liquid and 7.2wt% of 9wt% are prepared respectively according to method provided by embodiment one PVA and SA blend spinning liquid, wherein in PVA and CS blend spinning liquid the mass ratio of PVA and CS be 4:1, PVA and SA mixing The mass ratio of PVA and SA is 50:10 in spinning solution；

(2) it debugs electrostatic spinning machine: PVA the and CS blend spinning liquid prepared and PVA and SA blend spinning liquid is fallen respectively After entering the identical syringe of specification, metal needle is put upside down standing upwards, and bubble in syringe is made then to squeeze discharge toward rising, After bubble is discharged, syringe is mounted on spinning machine and is fixed；Syringe needle is connected to the conducting wire of high-pressure electrostatic again；It adjusts and receives dress Spinning electromechanical source is opened after the spinning distance set, after spinning parameter is set, press " perfusion acceleration " key, if any spinning solution from needle Head oozes, then position is adjusted successfully；If do not oozed, then need to continue to adjust；Open the power supply of reception device, connection ground Line, adjusting revolving speed are 3.2r/s, and reception device is allowed to run first；" perfusion starts " key of spinning machine is pressed, and it is quiet to open high pressure Power supply adjusts voltage to requiring spinning section；

The spinning condition of PVA and CS blend spinning liquid are as follows: spinning voltage 16kv；Rate of flooding is 0.8mL/h；Spinning away from From for 11cm；Spinning humidity is 45%；

The spinning condition of PVA and SA blend spinning liquid are as follows: spinning voltage 16kv；Rate of flooding is 0.4mL/h；Spinning away from From for 11cm；Spinning humidity is 45%；

Under above-mentioned spinning condition, PVA the and CS blend spinning of injection equivalent in the syringe of first Xiang Sanzhi same size Liquid works together, and the first PVA-CS spinning film is first received on the reception device, after reaching certain thickness；Then three Zhi Xiangtong are replaced The syringe of specification injects PVA the and SA blend spinning liquid of equivalent, continues spinning, on the basis of the first PVA-CS spinning film PVA-SA spinning film is continued to, in the case where sufficiently thick, then the syringe of three same sizes is replaced, injects the PVA of equivalent With CS blend spinning liquid, continue spinning, the 2nd PVA-CS spinning film is continued on the basis of PVA-SA spinning film, is superimposed structure At the composite membrane of " sandwich " structure；

(3) composite membrane is unloaded on the reception device, and clip specification is the sample of 5cm*5cm in the middle part of composite membrane；

Smooth foam is placed on to the bottom of air dryer, is placed on ventilation operation platform, and by the penta 2 of 50wt% The aqueous solution of aldehyde slowly pours into glass dish, and glass dish is slowly put into air dryer and is placed on foam, puts net into Frame puts air dryer into electric heating convection oven 37 DEG C of preheating 30min, takes out and be air-dried from electric drying oven with forced convection Device is placed on workbench, slowly pushes bottle cap until fully opening, closed workbench arranges glutaraldehyde gas in workbench Out, sample is gently placed on rack with tweezers, is closed the lid, slight friction ensures that air dryer seals back and forth, in electric heating 37 DEG C of constant temperature decatizes are for 24 hours in air dry oven；

The sample after drying is separated with aluminium-foil paper with tweezers, puts the ethanol solution for filling 3% calcium chloride of 15mL into Small beaker in, impregnate 1.5h；

Sample is taken out from small beaker with tweezers, is scrubbed 3 times in dehydrated alcohol, then be put into clean small beaker, The rim of a cup of small beaker is closed to pierce through preservative film with clean metal needle, be placed in vacuum oven and take out very with preservative film Sky is dry, obtains PVA-CS-SA spinning fibre film.

Fig. 1 is the structural schematic diagram for the PVA-CS-SA spinning fibre film that the present embodiment is prepared；Fig. 2 is the present embodiment What the PVA-CS spinning film and PVA-SA spinning film for the PVA-CS-SA spinning fibre film being prepared were observed under an optical microscope Picture, Fig. 2 (a) are PVA-CS spinning film, and Fig. 2 (b) is PVA-SA spinning film.

Embodiment three

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of PVA and CS blend spinning liquid of 7.5wt% and 6.5wt% in (1), wherein PVA and The mass ratio of PVA and CS is 3:1 in CS blend spinning liquid, and the mass ratio of PVA and SA is 10:3 in PVA and SA blend spinning liquid；

The spinning condition of PVA and CS blend spinning liquid in step (2) are as follows: spinning voltage 19kv；Rate of flooding is 0.9mL/h；Spinning distance is 11.5cm；Spinning humidity is 48%；

The spinning condition of PVA and SA blend spinning liquid are as follows: spinning voltage 17kv；Rate of flooding is 0.4mL/h；Spinning away from From for 11.5cm；Spinning humidity is 48%；

Using the aqueous solution of the glutaraldehyde of 45wt% in step (3), make sample 37 DEG C of constant temperature in electric drying oven with forced convection Decatize 23h；

In the small beaker of the ethanol solution of 2.5% calcium chloride of 15mL, 1.8h is impregnated；Remaining condition is all the same.

Example IV

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment one: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 8wt% and 6wt% in (1), wherein PVA and CS is mixed The mass ratio for closing PVA and CS in spinning solution is 4:1, and the mass ratio of PVA and SA is 50:6 in PVA and SA blend spinning liquid；

The spinning condition of PVA and CS blend spinning liquid in step (2) are as follows: spinning voltage 20kv；Rate of flooding is 1mL/ h；Spinning distance is 12cm；Spinning humidity is 50%；

The spinning condition of PVA and SA blend spinning liquid are as follows: spinning voltage 15kv；Rate of flooding is 0.3mL/h；Spinning away from From for 12cm；Spinning humidity is 50%；

Using the aqueous solution of the glutaraldehyde of 60wt% in step (3), make sample 37 DEG C of constant temperature in electric drying oven with forced convection Decatize 20h；

In the small beaker of the ethanol solution of 4% calcium chloride of 15mL, 1h is impregnated；Remaining condition is all the same.

Embodiment five

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment one: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 7wt% and 7.9wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 4:1 in blend spinning liquid, and the mass ratio of PVA and SA is 70:9 in PVA and SA blend spinning liquid；

The spinning condition of PVA and CS blend spinning liquid in step (2) are as follows: spinning voltage 15kv；Rate of flooding is 0.3mL/h；Spinning distance is 10cm；Spinning humidity is 40%；

The spinning condition of PVA and SA blend spinning liquid are as follows: spinning voltage 20kv；Rate of flooding is 0.5mL/h；Spinning away from From for 10cm；Spinning humidity is 40%；

Using the aqueous solution of the glutaraldehyde of 40wt% in step (3), make sample 37 DEG C of constant temperature in electric drying oven with forced convection Decatize 25h；

In the small beaker of the ethanol solution of 2% calcium chloride of 15mL, 3h is impregnated；Remaining condition is all the same.

Embodiment six

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 8.5wt% and 9wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 5:1 in blend spinning liquid, and the mass ratio of PVA and SA is 70:10 in PVA and SA blend spinning liquid；

The spinning condition of PVA and CS blend spinning liquid in step (2) are as follows: spinning voltage 17kv；Rate of flooding is 0.6mL/h；Spinning distance is 10.5cm；Spinning humidity is 46%；

The spinning condition of PVA and SA blend spinning liquid are as follows: spinning voltage 19kv, preferably 18-20kv；Rate of flooding is 0.5mL/h；Spinning distance is 10.5cm；Spinning humidity is 46%；

Using the aqueous solution of the glutaraldehyde of 55wt% in step (3), make sample 37 DEG C of constant temperature in electric drying oven with forced convection Decatize 22h；

In the small beaker of the ethanol solution of 3.5% calcium chloride of 15mL, 1.2h is impregnated；Remaining condition is all the same.

Embodiment seven

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 7wt% and 7.2wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 4:1 in blend spinning liquid, and the mass ratio of PVA and SA is 50:10 in PVA and SA blend spinning liquid；Its Remaining condition is all the same.

Embodiment eight

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 8wt% and 7.2wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 4:1 in blend spinning liquid, and the mass ratio of PVA and SA is 50:10 in PVA and SA blend spinning liquid；Its Remaining condition is all the same.

Embodiment nine

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment one: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 9wt% and 9wt% in (1), wherein PVA and CS is mixed The mass ratio for closing PVA and CS in spinning solution is 4:1, and the mass ratio of PVA and SA is 50:10 in PVA and SA blend spinning liquid；Remaining Condition is all the same.

Embodiment ten

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment one: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 9wt% and 6wt% in (1), wherein PVA and CS is mixed The mass ratio for closing PVA and CS in spinning solution is 4:1, and the mass ratio of PVA and SA is 50:10 in PVA and SA blend spinning liquid；Remaining Condition is all the same.

Embodiment 11

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 9wt% and 7.2wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 3:1 in blend spinning liquid, and the mass ratio of PVA and SA is 50:10 in PVA and SA blend spinning liquid；Its Remaining condition is all the same.

Embodiment 12

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 9wt% and 7.2wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 5:1 in blend spinning liquid, and the mass ratio of PVA and SA is 50:10 in PVA and SA blend spinning liquid；Its Remaining condition is all the same.

Embodiment 13

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 9wt% and 7.2wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 4:1 in blend spinning liquid, and the mass ratio of PVA and SA is 10:3 in PVA and SA blend spinning liquid；Its Remaining condition is all the same.

Embodiment 13

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 9wt% and 7.2wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 4:1 in blend spinning liquid, and the mass ratio of PVA and SA is 70:10 in PVA and SA blend spinning liquid；Its Remaining condition is all the same.

Comparative example one

This comparative example provides a kind of preparation method of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 3wt% and 3.6wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 4:1 in blend spinning liquid, and the mass ratio of PVA and SA is 50:10 in PVA and SA blend spinning liquid；Its Remaining condition is all the same.

Fig. 3 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that this comparative example is prepared The picture that film is observed under an optical microscope, Fig. 3 (a) are PVA-CS spinning film, and Fig. 3 (b) is PVA-SA spinning film.

Comparative example two

This comparative example provides a kind of preparation method of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 10wt% and 15wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 4:1 in blend spinning liquid, and the mass ratio of PVA and SA is 50:10 in PVA and SA blend spinning liquid；Its Remaining condition is all the same.

Fig. 4 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that this comparative example is prepared The picture that film is observed under an optical microscope, Fig. 4 (a) are PVA-CS spinning film, and Fig. 4 (b) is PVA-SA spinning film.

Comparative example three

This comparative example provides a kind of preparation method of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 9wt% and 7.2wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 2.5:1 in blend spinning liquid, and the mass ratio of PVA and SA is 5:20 in PVA and SA blend spinning liquid； Remaining condition is all the same.

Fig. 5 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that this comparative example is prepared The picture that film is observed under an optical microscope, Fig. 5 (a) are PVA-CS spinning film, and Fig. 5 (b) is PVA-SA spinning film.

Comparative example four

This comparative example provides a kind of preparation method of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly using PVA the and SA blend spinning liquid of the PVA and CS blend spinning liquid of 9wt% and 7.2wt% in (1), wherein PVA and CS The mass ratio of PVA and CS is 10:1 in blend spinning liquid, and the mass ratio of PVA and SA is 100:1 in PVA and SA blend spinning liquid； Remaining condition is all the same.

Fig. 6 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that this comparative example is prepared The picture that film is observed under an optical microscope, Fig. 6 (a) are PVA-CS spinning film, and Fig. 6 (b) is PVA-SA spinning film.

Comparative example five

This comparative example provides a kind of preparation method of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly in (2) PVA and CS blend spinning liquid spinning condition are as follows: spinning voltage 10kv；The spinning item of PVA and SA blend spinning liquid Part are as follows: spinning voltage 10kv；Remaining condition is all the same.

Fig. 7 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that this comparative example is prepared The picture that film is observed under an optical microscope, Fig. 7 (a) are PVA-CS spinning film, and Fig. 7 (b) is PVA-SA spinning film.

Comparative example six

This comparative example provides a kind of preparation method of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly in (2) PVA and CS blend spinning liquid spinning condition are as follows: spinning voltage 25kv；The spinning item of PVA and SA blend spinning liquid Part are as follows: spinning voltage 25kv；Remaining condition is all the same.

Fig. 8 is PVA-CS spinning film and the PVA-SA spinning for the PVA-CS-SA spinning fibre film that this comparative example is prepared The picture that film is observed under an optical microscope, Fig. 8 (a) are PVA-CS spinning film, and Fig. 8 (b) is PVA-SA spinning film.

Comparative example seven

This comparative example provides a kind of preparation method of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly in (3) using the aqueous solution of glutaraldehyde of 65wt%, making sample, 37 DEG C of constant temperature decatizes are for 24 hours in electric drying oven with forced convection；Its Remaining condition is all the same.

Comparative example eight

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment one: step Suddenly in (3) in the small beaker of the ethanol solution of 5% calcium chloride of 15mL, 1.5h is impregnated；Remaining condition is all the same.

Comparative example nine

This comparative example provides a kind of preparation method of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly in (3) using the aqueous solution of glutaraldehyde of 20wt%, making sample, 37 DEG C of constant temperature decatizes are for 24 hours in electric drying oven with forced convection；Its Remaining condition is all the same.

Comparative example ten

The preparation method for present embodiments providing a kind of PVA-CS-SA spinning fibre film, unlike embodiment two: step Suddenly in (3) in the small beaker of the ethanol solution of 1% calcium chloride of 15mL, 1.5h is impregnated；Remaining condition is all the same.

Test example one

(1) it will be done (after " taylor cone " 20min for keeping syringe needle) in the case where the spinning condition of each embodiment and comparative example is stablized Net glass slide, which is fixed in reception device, receives fiber, is received in front of the reception device at 2-3cm, after 2-3min, fetches load Slide sets the state of optical microphotograph microscopic observation fiber.

(2) swelling ratio and weight-loss ratio of spinning fibre film are tested

A. the sample that will be taken out in vacuum oven, weigh Wo respectively, makes a record.After weighing, each Small beaker sequentially adds the distilled water of 20mL, is placed in constant-temperature shaking incubator and impregnates, and temperature setting is impregnated for 24 hours at 37 DEG C.

B. after taking out small beaker, sample is picked up simultaneously with two tweezers, perpendicular on filter paper, until distilled water is no longer from sample It is flowed out in product, can weigh Wt, make a record.The calculation formula of swelling ratio is as follows:

Swelling ratio Q=(Wt-Wo)/Wo

C. weigh after, sample is put back to clean small beaker, with preservative film by the rim of a cup of small beaker close come, with do Net metal needle pierces through preservative film.It is placed in vacuum oven vacuum drying.It is completely dried to sample, takes out sample and claimed Wd is measured, is made a record.The calculation formula of weight-loss ratio is as follows:

Weight-loss ratio G=(Wo-Wd)/Wo

Test result is as shown in table 1.

The swelling ratio of 1 spinning fibre film of table and the test result of weight-loss ratio

As seen from the above table, method spinning provided by the embodiment of the present invention two to 14 is stablized, and fibre diameter is uniform, preparation Obtained spinning fibre film spinning fibre membrane swelling degree is high, and good hygroscopicity, color is whitened, and pliability is good, and weight-loss ratio is low, water resistant Property is good, is more suitable for medical dressing.Wherein, the performance for the spinning fibre film that method provided by embodiment two is prepared is most It is excellent.

Comparative example one is compared with embodiment two, and by Fig. 2 and 3, it can be concluded that, PVA and CS blend spinning liquid or PVA and SA are mixed , cannot be at silk when conjunction concentration of dope is too low, directly ejection spinning solution, string-of-pearls-like is more.

Comparative example two is compared with embodiment two, PVA and CS blend spinning liquid or PVA and SA are mixed it can be seen from Fig. 2 and 4 When conjunction concentration of dope is excessively high, it may appear that the diameter of fracture of wire, fiber is unstable, also will cause syringe needle blocking in spinning process.

Comparative example three is compared with embodiment two, and CS content is higher or when SA content is higher it can be seen from Fig. 2 and 5, more not Conducive to spinning, there are a large amount of string-of-pearls-like, or even directly spray spinning solution, causes the failure of spinning.

Comparative example four is compared with embodiment two, when PVA content is higher it can be seen from Fig. 2 and 6, is more conducive to spinning, still The swelling ratio that will lead to spinning fibre film is low, and hygroscopicity is poor.

Comparative example five is compared with embodiment two, and when voltage is lower it can be seen from Fig. 2 and 7, not up to spinning solution spinning is wanted The minimum voltage asked, fails to form spinneret, causes the failure of spinning.

Comparative example six is compared with embodiment two, when voltage is higher it can be seen from Fig. 2 and 8, it may appear that fracture of wire, string-of-pearls-like Increase, or even directly spray spinning solution, causes the failure of spinning.

Comparative example seven and comparative example eight compared with embodiment two, the concentration of aqueous solution of glutaraldehyde is higher or calcium chloride it is anhydrous When the concentration of ethanol solution is higher, makes composite membrane crosslinking excessively, cause spinning fibre film pliability poor, intensity is low.

Comparative example nine and comparative example ten compared with embodiment two, the concentration of aqueous solution of glutaraldehyde is lower or calcium chloride it is anhydrous When the concentration of ethanol solution is lower, it is not thorough composite membrane crosslinking, causes spinning fibre film weight-loss ratio high, water-resistance is poor.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims

1. a kind of preparation method of PVA-CS-SA spinning fibre film, which comprises the steps of:

(a) PVA and CS blend spinning liquid is obtained into the first PVA-CS spinning film through electrostatic spinning；Then PVA and SA is mixed and is spun Silk liquid obtains PVA-SA spinning film through electrostatic spinning, is superimposed upon PVA-SA spinning film on the first PVA-CS spinning film；Again will PVA and CS blend spinning liquid obtains the 2nd PVA-CS spinning film through electrostatic spinning, and the 2nd PVA-CS spinning film is made to be superimposed upon PVA- On SA spinning film, composite membrane is obtained；

2. the preparation method of PVA-CS-SA spinning fibre film according to claim 1, which is characterized in that the PVA and CS The concentration of blend spinning liquid is 7-9wt%, preferably 8-9wt%, further preferably 9wt%；

3. the preparation method of PVA-CS-SA spinning fibre film according to claim 1, which is characterized in that the PVA and CS The mass ratio of PVA and CS is (3-5): 1, preferably (4-5): 1, further preferably 4:1 in blend spinning liquid；

And/or the mass ratio of PVA and SA is (10-70): (3-10), preferably (50- in PVA the and SA blend spinning liquid 70): (6-10), further preferably 50:10.

4. the preparation method of PVA-CS-SA spinning fibre film according to claim 1, which is characterized in that the step (b) In, composite membrane is first reacted with cross-linking agents, then with complexing agent complex reaction, obtain PVA-CS-SA spinning fibre film；

The crosslinking agent includes dialdehyde or acid anhydrides, preferably dialdehyde, further preferably in glutaraldehyde, malonaldehyde or butanedial At least one is still more preferably glutaraldehyde；

The complexing agent includes soluble calcium salt, preferably at least one of calcium chloride, calcium sulfate or calcium nitrate, further excellent It is selected as calcium chloride.

5. the preparation method of PVA-CS-SA spinning fibre film according to claim 4, which is characterized in that the step (b) In, composite membrane is first reacted with the aqueous solution vapor crosslinking of glutaraldehyde, then the alcoholic solution complex reaction with calcium chloride, obtains PVA- CS-SA spinning fibre film；

Preferably, the concentration of the aqueous solution of the glutaraldehyde is 45-55wt%, preferably 50-55wt%；And/or crosslinking time For 20-25h, preferably 20-24h；

Preferably, the concentration of the alcoholic solution of the calcium chloride is 2-4wt%, preferably 3-4wt%；And/or crosslinking time 1- 3h, preferably 1.5-3h.

6. the preparation method of PVA-CS-SA spinning fibre film according to claim 1-5, which is characterized in that institute It states in step (a), the spinning condition of the PVA and CS blend spinning liquid are as follows: spinning voltage 15-20kv, preferably 16- 20kv；

And/or rate of flooding 0.3-1mL/h, preferably 0.8-1mL/h；

And/or spinning distance is 10-12cm, preferably 11-12cm；

And/or spinning humidity is 40-50%, preferably 45-50%.

7. the preparation method of PVA-CS-SA spinning fibre film according to claim 1-5, which is characterized in that institute It states in step (a), the spinning condition of the PVA and SA blend spinning liquid are as follows: spinning voltage 15-20kv, preferably 16- 20kv；

And/or rate of flooding 0.3-0.5mL/h, preferably 0.4-0.5mL/h；

And/or spinning distance is 10-12cm, preferably 11-12cm；

And/or spinning humidity is 40-50%, preferably 45-50%.

8. the preparation method of PVA-CS-SA spinning fibre film according to claim 1-5, which is characterized in that institute The preparation method for stating PVA and CS blend spinning liquid includes the following steps:

(l) PVA solution is obtained by PVA is soluble in water；

(m) CS is dissolved in acetic acid solution and obtains CS solution；

(o) PVA solution is obtained by PVA is soluble in water；

(p) SA solution is obtained by SA is soluble in water；

9. a kind of PVA-CS-SA spinning fibre film, which is characterized in that by the described in any item preparation method systems of claim 1-8 It is standby to obtain.

10. a kind of PVA-CS-SA spinning fibre film being prepared by the described in any item preparation methods of claim 1-8 or power Benefit require 9 described in PVA-CS-SA spinning fibre film preparing the application in medical dressing.