CN106632949A - Oligochitosan or derivative-modified polyurethane fiber dressing and preparation method thereof - Google Patents
Oligochitosan or derivative-modified polyurethane fiber dressing and preparation method thereof Download PDFInfo
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- CN106632949A CN106632949A CN201611199517.3A CN201611199517A CN106632949A CN 106632949 A CN106632949 A CN 106632949A CN 201611199517 A CN201611199517 A CN 201611199517A CN 106632949 A CN106632949 A CN 106632949A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
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- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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Abstract
The invention belongs to the technical field of biomedical materials, and discloses an oligochitosan or derivative-modified polyurethane fiber dressing and a preparation method thereof. The preparation method comprises the following steps: initiating ring opening polymerization of an alkynylation lactide monomer by adopting polyethylene glycol and synthesizing biodegradable polyester ether containing alkynyl in a side chain; taking the biodegradable polyester ether as a soft segment, reacting with diisocyanate and a chain extender to synthesize biodegradable polyurethane containing the alkynyl in the side chain; synthesizing oligosaccharide or a derivative thereof; carrying out clicking chemical reaction on the biodegradable polyurethane containing the alkynyl in the side chain and the oligosaccharide or the derivative thereof and synthesizing oligochitosan or derivative-modified polyurethane; and building the oligochitosan or derivative-modified polyurethane fiber dressing through an electrospinning technique. The polyurethane fiber dressing obtained by the method has good flexibility, tension resistance, hygroscopic property and breathability; due to the appropriate porous structure and a biological function of controlling bacterial infection and promoting wound repair, the polyurethane fiber dressing is expected to be widely used.
Description
Technical field
The invention belongs to the poly- ammonia of biology medical material technical field, more particularly to a kind of oligochitosan or derivatives thereof modification
Ester fiber dressing and preparation method.
Background technology
Wound healing is an important topic in the traumatology department, and the material for researching and developing preferable wound healing is standby
It is concerned.Traditional dressing such as gauze, Cotton Gossypii etc. easily breed bacteria, adhesion wound brings secondary insult during replacing.Therefore, it is domestic
The research of outer scholar Efforts To Develop new pattern compress in recent years, it is intended to avoid the shortcoming of traditional dressing.Generally, wound dressing not only will
Ask and protect fluidity, suitable mechanical strength and elasticity with good biocompatibility, imbibition, should also have every bacterium effect, in case
The only infection of wound surface, and the healing of wound surface can be promoted.Polyurethane material is because its is safe and nontoxic, non-stimulated, not sensitization, good
The characteristic such as biocompatibility well and mechanical property, is the more class wound dressing of research report both at home and abroad at present.However, single
One polyurethane medical dressing can not effectively prevent that wound surface is infected, accelerate wound repair, and easily stick together with wound surface,
Easily cause secondary insult.In recent years, there are many reports around the Patents and document for improving the various performances of polyurethane dressing.
The Chinese invention patent of application number 201510994613.6 disclose it is a kind of promotion skin wound repair dressing and
Preparation method, the composition and content of the dressing is as follows：Polyurethane 20～30, Herba seu Radix Calanthess 4～9, Rhizoma Drynariae 3～6, Fructus Forsythiae 8
～14, Radix Angelicae Sinensis 5～12, Herba Sambuci Chiensis 4～8, Herba Centellae 6～10, the Fructus Kochiae 8～12, Herba Caryopteridis Incanae 9～13, Radix Paeoniae Rubra 6～9, the Radix Astragali 4～
7, Polyethylene Glycol 12～17, glycerol 9～11, sulfanilamide 7～10.The dressing has promotion wound surface local blood circulation, mitigates wound
The characteristics such as face local swelling.And for example the Chinese invention patent of application number 201510490782.6 discloses a kind of the poly- of composite collagen
Urethano bilayer dressing, the dressing has the advantages that wound repair and reduction cicatrization can be promoted.
At present the modified of polyurethane dressing materials is concentrated mainly on using blending or compound waits physical modification method, introducing
Blending filler dispersibility, stability in the base etc. be all the time the subject matter for existing.Click chemistry is because of its reaction condition
Gently, quickly, effectively with high yield the features such as, strong research tool in material supply section scholar's handss is become in recent years, and gradually should
Use the aspects such as the modifying and decorating of all kinds of polymeric materials.If click chemistry this advanced technology can be flexibly utilized by polyurethane
Dressing is designed and modification biology in molecular level, and this will provide one for the exploitation of new polyurethane dressing with application
Effective and brand-new approach.
Oligochitosan is to be produced Jing after hydrolysis by shitosan, be formed by connecting by β -1-4 glycosidic bonds by 2～10 Portugal's D-glucosamine
Oligosaccharide, its relative molecular mass is little, good water solubility, can be absorbed by tissue utilization.Oligochitosan not only has shitosan excellent
Biological function, such as good antibacterial, hemostasis, antioxidation, anticancer physiologically active can promote cell differentiation and growth,
Promote wound epithelization, form granulation tissue, accelerate the healing of wound, and fibrous connective tissue can be suppressed, reduce cicatrix
Organize the formation of and promote vascular endothelial cell growth etc.；And, the biological function of oligochitosan is often substantially better than shitosan.Cause
This, oligochitosan and its related derivatives become in recent years the focus of research and product development both at home and abroad.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art with it is not enough, the primary and foremost purpose of the present invention be provide a kind of oligochitosan or
The preparation method of the polyurethane fiber dressing of its Derivatives Modified.The inventive method by the syntheti c route of designing material, flexibly
With click chemistry, the polyurethane fiber dressing of class oligochitosan or derivatives thereof modification is efficiently obtained under mild conditions.
Another object of the present invention is the polyurethane fiber for providing oligochitosan prepared by said method or derivatives thereof modification
Dressing.
The purpose of the present invention is realized by following proposal：
A kind of preparation method of the polyurethane fiber dressing of oligochitosan or derivatives thereof modification, comprises the following steps：
Step one：Alkynyl lactide monomers ring-opening polymerisation is caused using Polyethylene Glycol, synthesizing biology of the side chain containing alkynyl can
Degraded polyester ether；
Step 2：With biodegradable polyesters ether of the side chain containing alkynyl as soft section, with diisocyanate and chain extender reaction
Biodegradable polyurethane of the synthesis side chain containing alkynyl；
Step 3：Synthesis Azide oligochitosan or derivatives thereof；
Step 4：There is clickization in Biodegradable polyurethane of the side chain containing alkynyl and Azide oligochitosan or derivatives thereof
Reaction is learned, synthesizes the polyurethane of oligochitosan or derivatives thereof modification；
Step 5：The polyurethane fiber dressing of oligochitosan or derivatives thereof modification is built by electrostatic spinning technique.
In step one, the polymerizing condition of the biodegradable polyesters ether of the synthesis side chain containing alkynyl is preferably：Catalyst
From stannous octoate, catalyst amount is 0.01～0.3mol% of alkynyl lactide monomers consumption, and reaction temperature is 80～150
DEG C, the response time is 6～54h.
The Polyethylene Glycol is with the molar feed ratio of alkynyl lactide：1:5～1:50.
The range of number-average molecular weight of the Polyethylene Glycol is：200～4000.
The general structure of the alkynyl lactide monomers is as shown in (I)：
Wherein, R1、R2、R3And R4What is may be the same or different is respectively hydrogen atom, methyl or alkynyl, and R1、R2、R3And R4Extremely
Rare one is alkynyl.
In step 2, the synthesis of Biodegradable polyurethane of the side chain containing alkynyl is the life containing alkynyl by side chain
Biodegradable polyester ether is obtained with diisocyanate and chain extender reaction, the step that preparation method is prepared using conventional polyurethanes
Method or two-step method, actual conditions can be：
The side chain contains the molar feed ratio of the biodegradable polyesters ether, diisocyanate and chain extender of alkynyl：
1:(2～10):(1～6)；
It is different that described diisocyanate is preferably hexamethylene diisocyanate, dicyclohexyl diisocyanate, toluene two
Cyanate etc.；
Described chain extender is preferably ethylene glycol, 1,4- butanediols, diglycol, ethylenediamine, 1,4- butanediamine etc..
In step 3, described Azide oligochitosan or derivatives thereof is by oligochitosan or derivatives thereof and Hydrazoic acid,sodium salt
Reaction is prepared, and its preparation method is this area conventional method, specifically may include following steps：(1) by oligochitosan or
Its derivant is soluble in water, adds dodecyl sodium sulfate, and both mol ratios are 1:1～1:10, at room temperature reaction 0.5～
8h, lyophilization obtains oligochitosan of alkyl sulfonic acid or derivatives thereof.(2) it is alkyl sulfonic acid oligochitosan or derivatives thereof is molten
In dimethylformamide, p-methyl benzene sulfonic chloride is added, both mol ratios are 1:1～1:30, add catalyst 4- diaminourea
Pyridine, catalyst amount is the 0.5～5% of oligochitosan or derivatives thereof quality, react in -20-40 DEG C 4 under nitrogen protection～
12h, obtains product.(3) in dimethylformamide, in molar ratio 1:1～1:50 rate of charge adds the reaction of step (2) to produce
Thing and Hydrazoic acid,sodium salt, 2～12h is reacted in 60～120 DEG C, and after reaction terminates, product is purified and is vacuum dried, that is, obtain nitrine
Change oligochitosan or derivatives thereof.
Described oligochitosan or derivatives thereof is preferably oligochitosan, chitooligosaccharidequaternary quaternary ammonium salt.
In step 4, Biodegradable polyurethane of the side chain containing alkynyl and Azide oligochitosan or derivatives thereof occur
The concrete operations of click chemistry reaction may include following steps：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell
Oligosaccharide or derivatives thereof is dissolved in organic solvent, and both mol ratios are 20:1～1:20；Above-mentioned mixed solution is added to and is contained
In the organic solvent of catalyst, 6～36h of reacting at normal temperature without light obtains the polyurethane of described oligochitosan or derivatives thereof modification.
Described catalyst can be Cu-lyt. (CuBr), or mol ratio is 1:1 copper sulfate and ascorbic acid are mixed
One kind in compound.
The consumption of the catalyst is preferably the 1～20% of Biodegradable polyurethane mole of the side chain containing alkynyl.
Described organic solvent can be at least one in tetrahydrofuran, N,N-dimethylformamide and dimethyl sulfoxide.
In step 5, the electrostatic spinning technique builds the system of the polyurethane fiber dressing of oligochitosan or derivatives thereof modification
Preparation Method is as follows：The polyurethane that oligochitosan or derivatives thereof is modified is dissolved in organic solvent, mass-volume concentration is obtained for 5
～20% Electrospun solution, carries out spinning under the electrostatic pressure of 10～30kV.
Described organic solvent can be at least one in tetrahydrofuran, N,N-dimethylformamide and dimethyl sulfoxide.
The present invention provides the polyurethane fiber dressing of oligochitosan that said method is prepared or derivatives thereof modification.This
Oligochitosan with various Biofunctionals or derivatives thereof is incorporated into polyurethane dressing by bright method by the combination of chemical bond
In, so as to give the excellent hydrophilic of dressing of the present invention, antibacterial, antiinflammatory, hemostasis, promotion cell differentiation and wound tissue formation etc.
Biofunctional, it not only has good pliability and tension stress, suitable loose structure, good water suction and breathability,
And, the biological function with control bacterium infection and promotion wound repair, therefore, oligochitosan of the present invention or derivatives thereof
The polyurethane fiber dressing of modification is expected extensively to be applied.
The present invention has the following advantages and beneficial effect relative to prior art：
(1) present invention can using the biology of simple, easy technology path design synthesis oligochitosan or derivatives thereof modification
Degradable polyurethane, and realize distribution and density controllable of the oligochitosan or derivatives thereof in biodegradable polyurethane side chain.
(2) because the high specificity and reaction condition of click chemistry reaction are gentle, in the present invention without the need for oligochitosan or
Other groups in its derivant are protected.
(3) present invention under mild conditions, by the combination of chemical bond by the oligochitosan with various Biofunctionals
Or derivatives thereof be incorporated in polyurethane dressing, so as to give the excellent hydrophilic of polyurethane dressing, antibacterial, antiinflammatory, hemostasis, rush
Enter the Biofunctional such as cell differentiation and wound tissue formation.
(4) preparation condition according to the present invention is gentle, and the new polyurethane fiber dressing of preparation not only has good soft
Toughness and tension stress, suitable loose structure, good water suction and breathability, and, with control bacterium infection and promotion wound
The biological function that face is repaired, therefore, the polyurethane fiber dressing for being obtained is expected extensively to be applied.
Description of the drawings
Fig. 1 is the surface contact angle of PU and COS-PU fiber dressing prepared in the embodiment of the present invention 1.
Fig. 2 is PU and COS-PU fiber dressing surface fibroblast cell adhesions prepared in the embodiment of the present invention 5
The distribution of pattern and nucleus laser co-focusing photo.
Fig. 3 is PU and G-COS-PU fiber dressing surfaces fibroblast adhesion prepared in the embodiment of the present invention 6
The stereoscan photograph of pattern.
Fig. 4 is PU and G-COS-PU fiber dressing surface escherichia coli prepared in the embodiment of the present invention 8 and golden yellow
The stereoscan photograph that glucose coccus stick and breed.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
If no special instructions, all raw materials and reagent are conventional raw material, the reagent in market in the following example.
Embodiment 1：
Step 1：With stannous octoate as catalyst, Polyethylene Glycol (3g, Mn=400) cause alkynyl for macromole evocating agent
Glycolide monomer (17.5g) body ring-opening polymerisation, stannous octoate consumption is the 0.05mol% of alkynyl glycolide monomer consumption,
Reaction temperature：100 DEG C, the response time：24h.After reaction terminates, crude product chloroform dissolves, dehydrated alcohol precipitation, then
48h is vacuum dried in 40 DEG C, biodegradable polyesters ether of the side chain containing alkynyl is obtained.
Step 2：Weigh biodegradable polyesters ether of the 5g step 1 gained side chain containing alkynyl and be dissolved in N,N-dimethylformamide
It is placed in four-hole boiling flask, leads to nitrogen, and is heated to 100 DEG C；The hexamethylene diisocyanate of 2.5g is subsequently adding, 100
React at DEG C and performed polymer is obtained after 4h；Finally, the chain extender BDO and appropriate catalyst dibutyltin cinnamic acid of 1.2g are added
Dibutyl tin, continues to react 2h at 100 DEG C.After reaction terminates, purified biology of the side chain containing alkynyl that obtain of crude product can drop
Solution polyurethane.
Step 3：(1) by 6g oligochitosan (Mw=1000Da) deionized water is dissolved in, add dodecyl sodium sulfate, two
Person's mol ratio is 1:2,2h is reacted at room temperature, lyophilization obtains the oligochitosan of alkyl sulfonic acid.(2) by above-mentioned gained alkyl
Sulfonated oligochitosan is dissolved in DMF, adds p-methyl benzene sulfonic chloride, and both press 1:5 mol ratio feeds intake, then
Catalyst 4- diamino-pyridines, catalyst amount is added to be the 1.5% of oligochitosan quality, 8h is reacted at 0 DEG C under nitrogen protection,
The purified process of product.(3) in DMF, by 1:10 rate of charge adds the solid of above-mentioned synthesis to produce
Thing and Hydrazoic acid,sodium salt, react 6h at 80 DEG C, and after reaction terminates, product is purified and is vacuum dried, that is, obtain Azide shell few
Sugar.
Step 4：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell obtained by step 2 and step 3 difference
Oligosaccharide is dissolved in tetrahydrofuran, and both mol ratios are 1:1；Then polymer solution is added to containing CuBr's under nitrogen protection
In tetrahydrofuran, reacting at normal temperature without light 24h obtains the polyurethane of oligochitosan modification.
Step 5：The polyurethane (2g) of the oligochitosan modification of step 4 gained is dissolved in into tetrahydrofuran and N, N- dimethyl methyl
(volume ratio is 5 in amide solvent pairs:5), obtain the Electrospun solution that mass-volume concentration is 12.5%, through magnetic agitation,
Electrospun liquid supplying device is injected after ultrasonic disperse, spinning is carried out under the electrostatic pressure of 15kV, finally obtain oligochitosan modification
Polyurethane fiber dressing.Equally pure polyurethane (commercially available, purchase) fiber dressing is built using electrostatic spinning technique.
The oligochitosan to the pure polyurethane fiber dressing (PU) of electrostatic spinning and above-mentioned synthesis is determined by surface contact angle to repair
The hydrophilic of the polyurethane fiber dressing (COS-PU) of decorations is tested, and test result is shown in Fig. 1.Data display in figure, pure PU
The water contact angle of fibrous membrane is up to 122.3 ± 2.3 °, shows that pure PU fibrous membranes are more hydrophobic；However, the water of COS-PU fibrous membranes
As little as 72.8 ± 1.7 ° of contact angle, illustrating the hydrophilic on fibrous membrane surface is substantially improved.Conversely, with diiodomethane as drop
Phase, the liquid-drop contact angle on pure PU fibrous membranes is 8.3 ± 1.4 °, and the liquid-drop contact angle on COS-PU fibrous membranes surface is up to
46.4±1.6°.Data above illustrates to modify PU fibrous membranes using oligochitosan, can significantly improve the parent on PU fibrous membranes surface
Aqueouss, are conducive to it to be preferably applied for Wound dressing.
Embodiment 2：
Step 1：With stannous octoate as catalyst, Polyethylene Glycol (5g, Mn=1000) cause alkynyl for macromole evocating agent
Change glycolide monomer (22.5g) body ring-opening polymerisation, stannous octoate consumption is alkynyl glycolide monomer consumption
0.05mol%, reaction temperature is 120 DEG C, and the response time is 18h.After reaction terminates, reacting coarse product chloroform dissolves,
Dehydrated alcohol is precipitated, and is then vacuum dried 36h in 40 DEG C, obtains biodegradable polyesters ether of the side chain containing alkynyl.
Step 2：Weigh biodegradable polyesters ether of the 5g step 1 gained side chain containing alkynyl and be dissolved in N,N-dimethylformamide
It is placed in four-hole boiling flask, leads to nitrogen, and is heated to 120 DEG C；It is subsequently adding the dicyclohexyl diisocyanate and 1.0g of 3.5g
Ethylene glycol, react 5h at 120 DEG C.After reaction terminates, crude product is purified to obtain biodegradable poly of the side chain containing alkynyl
Urethane.
Step 3：(1) by 5g oligochitosan (Mw=3000Da) deionized water is dissolved in, add dodecyl sodium sulfate, two
Person's mol ratio is 1:5,4h is reacted at room temperature, lyophilization obtains the oligochitosan of alkyl sulfonic acid.(2) by above-mentioned gained alkyl
Sulfonated oligochitosan is dissolved in DMF, adds p-methyl benzene sulfonic chloride, and both press 1:10 mol ratio feeds intake, then
Catalyst 4- diamino-pyridines, catalyst amount is added to be the 2.5% of oligochitosan quality, react at 10 DEG C under nitrogen protection
6h, the purified process of product.(3) in DMF, in molar ratio 1:15 rate of charge adds above-mentioned conjunction
Into solid product and Hydrazoic acid,sodium salt, react 5h at 80 DEG C, after reaction terminates, product is purified and vacuum drying, that is, obtain
Azide oligochitosan.
Step 4：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell obtained by step 2 and step 3 difference
Oligosaccharide is dissolved in DMF, and both mol ratios are 5:1；Then polymer solution is added under nitrogen protection
In DMF containing CuBr, reacting at normal temperature without light 12h obtains the polyurethane of oligochitosan modification.
Step 5：The polyurethane (3.5g) of the oligochitosan modification of step 4 gained is dissolved in into tetrahydrofuran and dimethyl formyl
(volume ratio is 3 in amine solvent pairs:7) the Electrospun solution that mass-volume concentration is 10%, is obtained, through magnetic agitation, ultrasound
Electrospun liquid supplying device is injected after dispersion, spinning is carried out under the electrostatic pressure of 20kV, finally obtain the poly- ammonia of oligochitosan modification
Ester fiber dressing.
Embodiment 3：
Step 1：With stannous octoate as catalyst, Polyethylene Glycol (5.5g, Mn=2000) cause alkynes for macromole evocating agent
Base glycolide monomer (20g) body ring-opening polymerisation, stannous octoate consumption is the 0.1mol% of alkynyl glycolide monomer consumption,
Reaction temperature：120 DEG C, the response time：24h.After reaction terminates, crude product chloroform dissolves, dehydrated alcohol precipitation, then
24h is vacuum dried in 40 DEG C, biodegradable polyesters ether of the side chain containing alkynyl is obtained.
Step 2：Weigh biodegradable polyesters ether of the 4.5g step 1 gained side chain containing alkynyl to be dissolved in tetrahydrofuran and be placed in
In four-hole boiling flask, lead to nitrogen, and be heated to 110 DEG C；The toluene di-isocyanate(TDI) of 1.8g is subsequently adding, at 120 DEG C 2h is reacted
Performed polymer is obtained afterwards；Finally, the chain extender diglycol of 1.0g is added, continues to react 3h at 120 DEG C.Reaction terminates
Afterwards, crude product is purified obtains Biodegradable polyurethane of the side chain containing alkynyl.
Step 3：(1) by 3g oligochitosan (Mw=3000) be dissolved in deionized water, dodecyl sodium sulfate is added, both
Mol ratio is 1:8,1h is reacted at room temperature, lyophilization obtains the oligochitosan of alkyl sulfonic acid.(2) by above-mentioned gained alkyl sulphur
Acidifying oligochitosan is dissolved in DMF, adds p-methyl benzene sulfonic chloride, and both press 1:5 mol ratio feeds intake, then adds
Enter catalyst 4- diamino-pyridines, catalyst amount is the 1.0% of oligochitosan quality, 5h is reacted at 20 DEG C under nitrogen protection,
The purified process of product.(3) in DMF, in molar ratio 1:5 rate of charge adds above-mentioned synthesis
Solid product and Hydrazoic acid,sodium salt, react 3h at 100 DEG C, and after reaction terminates, product is purified and is vacuum dried, that is, obtain nitrine
Change oligochitosan.
Step 4：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell obtained by step 2 and step 3 difference
Oligosaccharide is dissolved in tetrahydrofuran, and both mol ratios are 10:1；Then under nitrogen protection polymer solution is added to into sulfur acid
(mol ratio is 1 for copper and ascorbic acid：1) in tetrahydrofuran, reacting at normal temperature without light 6h obtains the polyurethane of oligochitosan modification.
Step 5：During the polyurethane (4g) of the oligochitosan modification of step 4 gained is dissolved in into DMF, obtain
To the Electrospun solution that mass-volume concentration is 15%, Electrospun liquid supplying device is injected after magnetic agitation, ultrasonic disperse,
Spinning is carried out under the electrostatic pressure of 25kV, the polyurethane fiber dressing of oligochitosan modification is finally obtained.Equally adopt electrostatic spinning
The pure polyurethane of technique construction (commercially available, purchase) fiber dressing.
Have studied the polyurethane fiber of the oligochitosan modification of the pure polyurethane fiber dressing (PU) of electrostatic spinning and above-mentioned synthesis
Suppression of the dressing (COS-PU) to gram negative bacteria (escherichia coli) and gram positive bacteria (staphylococcus glucose coccus) is given birth to
Long ability.Bacteriostatic experiment result shows that COS-PU fibrous membranes suppress the growth of escherichia coli and staphylococcus glucose coccus notable
Better than corresponding pure PU fibrous membranes, show, polyurethane is modified using oligochitosan, the biocidal property for improving polyurethane material can be limited
Energy.
Table 1PU and COS-PU fibrous membrane is to escherichia coli and staphylococcus aureuses bacteriostasis rate
Embodiment 4：
Step 1：With stannous octoate as catalyst, Polyethylene Glycol (5g, Mn=2000) cause alkynyl for macromole evocating agent
Change lactide monomer (12.5g) body ring-opening polymerisation, stannous octoate consumption is alkynyl lactide monomer consumption
0.15mol%, reaction temperature：130 DEG C, the response time：36h.After reaction terminates, crude product chloroform dissolves, anhydrous second
Alcohol is precipitated, and is then vacuum dried 48h in 40 DEG C, obtains biodegradable polyesters ether of the side chain containing alkynyl.
Step 2：Weigh biodegradable polyesters ether of the 4g step 1 gained side chain containing alkynyl to be dissolved in chloroform and be placed in four
In mouthful flask, lead to nitrogen, and be heated to 100 DEG C；The hexamethylene diisocyanate of 1.5g is subsequently adding, is reacted at 100 DEG C
Performed polymer is obtained after 4h；Finally, the chain extender diglycol and appropriate catalyst dibutyltin cinnamic acid dibutyl of 0.8g are added
Stannum, continues to react 3h at 100 DEG C.After reaction terminates, crude product is purified to obtain biodegradable poly ammonia of the side chain containing alkynyl
Ester.
Step 3：(1) by 5g oligochitosan (Mw=3000) be dissolved in deionized water, add a certain amount of dodecyl sulphur
Sour sodium, both mol ratios are 1:4,0.5h is reacted at room temperature, lyophilization obtains the oligochitosan of alkyl sulfonic acid.(2) will be upper
State gained alkyl sulfonic acid oligochitosan and be dissolved in DMF, add p-methyl benzene sulfonic chloride, both press 1:3 mole
Than feeding intake, catalyst 4- diamino-pyridines are added, catalyst amount is the 2.0% of oligochitosan quality, in 0 DEG C under nitrogen protection
Lower reaction 8h, the purified process of product.(3) in DMF, in molar ratio 1:12 rate of charge is added
The solid product and Hydrazoic acid,sodium salt of above-mentioned synthesis, reacts 5h at 90 DEG C, and after reaction terminates, product is purified and is vacuum dried,
Obtain Azide oligochitosan.
Step 4：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell obtained by step 2 and step 3 difference
Oligosaccharide is dissolved in tetrahydrofuran, and both mol ratios are 1:2；Then polymer solution is added to containing CuBr's under nitrogen protection
In tetrahydrofuran, reacting at normal temperature without light 18h obtains the polyurethane of oligochitosan modification.
Step 5：The polyurethane (3g) of the oligochitosan modification of step 4 gained is dissolved in into tetrahydrofuran and N, N- dimethyl methyl
(volume ratio is 2 in amide solvent pairs:8), obtain the Electrospun solution that mass-volume concentration is 10.0%, through magnetic agitation,
Electrospun liquid supplying device is injected after ultrasonic disperse, spinning is carried out under the electrostatic pressure of 15kV, finally obtain oligochitosan modification
Polyurethane fiber dressing.
Embodiment 5：
Step 1：With stannous octoate as catalyst, Polyethylene Glycol (3g, Mn=1000) cause alkynyl for macromole evocating agent
Change lactide monomer (12.5g) body ring-opening polymerisation, stannous octoate consumption is alkynyl glycolide monomer consumption
0.15mol%, reaction temperature：130 DEG C, the response time：24h.After reaction terminates, crude product chloroform dissolves, anhydrous second
Alcohol is precipitated, and is then vacuum dried 24h in 40 DEG C, obtains biodegradable polyesters ether of the side chain containing alkynyl.
Step 2：Weigh biodegradable polyesters ether of the 2.5g step 1 gained side chain containing alkynyl and be dissolved in N, N- dimethyl formyls
Amine is placed in four-hole boiling flask, leads to nitrogen, and is heated to 120 DEG C；The hexamethylene diisocyanate of 1.2g is subsequently adding,
React at 120 DEG C and performed polymer is obtained after 4h；Finally, the chain extender Putriscine of 0.7g is added, continues to react at 120 DEG C
3h.After reaction terminates, crude product is purified to obtain Biodegradable polyurethane of the side chain containing alkynyl.
Step 3：(1) by 2.5g oligochitosan (Mw=5000) be dissolved in deionized water, add dodecyl sodium sulfate, two
Person's mol ratio is 1:8,2h is reacted at room temperature, lyophilization obtains the oligochitosan of alkyl sulfonic acid.(2) by above-mentioned gained alkyl
Sulfonated oligochitosan is dissolved in DMF, adds p-methyl benzene sulfonic chloride, and both press 1:12 mol ratio feeds intake, then
Catalyst 4- diamino-pyridines, catalyst amount is added to be the 2.0% of oligochitosan quality, 7h is reacted at 0 DEG C under nitrogen protection,
The purified process of product.(3) in DMF, in molar ratio 1:10 rate of charge adds above-mentioned synthesis
Solid product and Hydrazoic acid,sodium salt, react 6h at 90 DEG C, and after reaction terminates, product is purified and is vacuum dried, that is, obtain nitrine
Change oligochitosan.
Step 4：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell obtained by step 2 and step 3 difference
Oligosaccharide is dissolved in tetrahydrofuran, and both mol ratios are 1:12；Then under nitrogen protection polymer solution is added to into sulfur acid
(mol ratio is 1 for copper and ascorbic acid：1) in tetrahydrofuran, reacting at normal temperature without light 15h obtains the polyurethane of oligochitosan modification.
Step 5：The polyurethane (2.5g) of the oligochitosan modification of step 4 gained is dissolved in into N, in N- dimethyl sulfoxide, is obtained
To the Electrospun solution that mass-volume concentration is 10%, Electrospun liquid supplying device is injected after magnetic agitation, ultrasonic disperse,
Spinning is carried out under the electrostatic pressure of 15kV, the polyurethane fiber dressing of oligochitosan modification is finally obtained.Equally adopt electrostatic spinning
The pure polyurethane of technique construction (commercially available, purchase) fiber dressing.
The oligochitosan modification of the pure polyurethane fiber dressing (PU) of electrostatic spinning and above-mentioned synthesis is observed using laser co-focusing
Polyurethane fiber dressing (COS-PU) surface it is fibroblastic stick pattern and nuclear distribution, as a result see Fig. 2.From
It is visible in figure, fibroblast COS-PU fiber dressing surfaces stick area and nuclear quantity is significantly higher than accordingly
PU fiber dressing on fibroblast, this shows that the dressing of COS-PU fibers is more beneficial for fibroblast compared with PU fiber dressing
Stick and grow, in other words, the dressing of COS-PU fibers is more beneficial for the healing of wound surface compared with PU dressing.
Embodiment 6：
Step 1：With stannous octoate as catalyst, Polyethylene Glycol (3g, Mn=1000) cause alkynyl for macromole evocating agent
Change glycolide monomer (15.5g) body ring-opening polymerisation, stannous octoate consumption is alkynyl glycolide monomer consumption
0.05mol%, reaction temperature：100 DEG C, the response time：24h.After reaction terminates, crude product chloroform dissolves, anhydrous second
Alcohol is precipitated, and is then vacuum dried 48h in 40 DEG C, obtains biodegradable polyesters ether of the side chain containing alkynyl.
Step 2：Weigh biodegradable polyesters ether of the 3g step 1 gained side chain containing alkynyl and be dissolved in dimethylformamide juxtaposition
In four-hole boiling flask, lead to nitrogen, and be heated to 100 DEG C；The dicyclohexyl diisocyanate of 1.5g is subsequently adding, at 100 DEG C
Performed polymer is obtained after reaction 4h；Finally, the glycol chain extender and appropriate catalyst dibutyltin dilaurylate of 0.6g are added,
Continue to react 2h at 100 DEG C.After reaction terminates, crude product is purified to obtain Biodegradable polyurethane of the side chain containing alkynyl.
Step 3：(1) by 4g chitooligosaccharidequaternary quaternary ammonium salt (Mw=1150) be dissolved in deionized water, add dodecyl sodium sulfonate
Sodium, both mol ratios are 1:3,4h is reacted at room temperature, lyophilization obtains the chitooligosaccharidequaternary quaternary ammonium salt of alkyl sulfonic acid.(2) will
Above-mentioned gained alkyl sulfonic acid chitooligosaccharidequaternary quaternary ammonium salt is dissolved in DMF, adds p-methyl benzene sulfonic chloride, and both press
1:5 mol ratio feeds intake, and adds catalyst 4- diamino-pyridines, and catalyst amount is the 1.5% of chitooligosaccharidequaternary quaternary ammonium salt quality,
7h, the purified process of product are reacted at 0 DEG C under nitrogen protection.(3) in DMF, in molar ratio 1:
5 rate of charge adds the solid product and Hydrazoic acid,sodium salt of above-mentioned synthesis, and 6h is reacted at 85 DEG C, and after reaction terminates, product Jing is pure
Change and be vacuum dried, that is, obtain Azide oligochitosan.
Step 4：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell obtained by step 2 and step 3 difference
Oligosaccharide quaternary ammonium salt is dissolved in tetrahydrofuran, then under nitrogen protection polymer solution is added to into sulfur acid copper and ascorbic acid
(mol ratio is 1:1) in tetrahydrofuran, reacting at normal temperature without light 24h obtains the polyurethane of chitooligosaccharidequaternary quaternary ammonium salt modification.
Step 5：The polyurethane (2g) of the chitooligosaccharidequaternary quaternary ammonium salt modification of step 4 gained is dissolved in into tetrahydrofuran and N, N- bis-
(volume ratio is 3 in methylformamide solvent pairs:7) the Electrospun solution that mass-volume concentration is 12.5%, is obtained, through magnetic force
Electrospun liquid supplying device is injected after stirring, ultrasonic disperse, spinning is carried out under the electrostatic pressure of 15kV, finally obtain oligochitosan season
The polyurethane fiber dressing of ammonium salt modification.Equally pure polyurethane (commercially available, purchase) fiber dressing is built using electrostatic spinning technique.
Fig. 3 is that the polyurethane of the chitooligosaccharidequaternary quaternary ammonium salt modification of electrostatic spinning polyurethane fiber dressing (PU) and above-mentioned synthesis is fine
The fibroblastic stereoscan photograph for sticking pattern in dimension dressing (G-COS-PU) surface.It can be seen that fibroblast
Stick in the dressing of PU fibers and G-COS-PU fiber dressing surfaces it is good with proliferative conditions, and as time went on, cell it is glutinous
Attached area and quantity are significantly increased, and this shows that introduce a certain amount of chitooligosaccharidequaternary quaternary ammonium salt in PU fibers dressing surface sticks to cell
Echo propagation to have no significant effect.
Embodiment 7：
Step 1：With stannous octoate as catalyst, Polyethylene Glycol (3g, Mn=2000) cause alkynyl for macromole evocating agent
Change glycolide monomer (10.5g) body ring-opening polymerisation, stannous octoate consumption is the 0.1mol% of alkynyl glycolide monomer consumption,
Reaction temperature：110 DEG C, the response time：24h.After reaction terminates, crude product chloroform dissolves, dehydrated alcohol precipitation, then
48h is vacuum dried in 40 DEG C, biodegradable polyesters ether of the side chain containing alkynyl is obtained.
Step 2：Weigh biodegradable polyesters ether of the 2.5g step 1 gained side chain containing alkynyl to be dissolved in chloroform and be placed in
In four-hole boiling flask, lead to nitrogen, and be heated to 100 DEG C；It is subsequently adding hexamethylene diisocyanate, the chain extender of 0.8g of 1.5g
BDO and appropriate catalyst dibutyltin dilaurylate, continue to react 2h at 100 DEG C.It is thick to produce after reaction terminates
Thing is purified to obtain Biodegradable polyurethane of the side chain containing alkynyl.
Step 3：(1) by 4g chitooligosaccharidequaternary quaternary ammonium salt (Mw=3205) be dissolved in deionized water, add dodecyl sodium sulfonate
Sodium, both mol ratios are 1:6,4h is reacted at room temperature, lyophilization obtains the chitooligosaccharidequaternary quaternary ammonium salt of alkyl sulfonic acid.(2) will
Above-mentioned gained alkyl sulfonic acid chitooligosaccharidequaternary quaternary ammonium salt is dissolved in DMF, adds a certain amount of to Methyl benzenesulfonyl
Chlorine, both press 1:8 mol ratio feeds intake, and adds catalyst 4- diamino-pyridines, and catalyst amount is chitooligosaccharidequaternary quaternary ammonium salt matter
The 2.0% of amount, under nitrogen protection 6h, the purified process of product are reacted at 10 DEG C.(3) in N,N-dimethylformamide
In, in molar ratio 1:6 rate of charge adds the solid product and Hydrazoic acid,sodium salt of above-mentioned synthesis, and 5h, reaction knot are reacted at 90 DEG C
Shu Hou, product is purified and is vacuum dried, that is, obtain Azide oligochitosan.
Step 4：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell obtained by step 2 and step 3 difference
Oligosaccharide quaternary ammonium salt is dissolved in tetrahydrofuran, then under nitrogen protection polymer solution is added to into the cuprous tetrahydrofuran of chloride containing
In, reacting at normal temperature without light 36h obtains the polyurethane of chitooligosaccharidequaternary quaternary ammonium salt modification.
Step 5：The polyurethane (2.5g) of the chitooligosaccharidequaternary quaternary ammonium salt modification of step 4 gained is dissolved in into tetrahydrofuran and N, N-
(volume ratio is 5 in dimethylformamide solvent pairs:5) the Electrospun solution that mass-volume concentration is 10%, is obtained, through magnetic force
Electrospun liquid supplying device is injected after stirring, ultrasonic disperse, spinning is carried out under the electrostatic pressure of 10kV, finally obtain oligochitosan season
The polyurethane fiber dressing of ammonium salt modification.Equally pure polyurethane (commercially available, purchase) fiber dressing is built using electrostatic spinning technique.
With Cavia porcelluss as experimental animal, carry out material and the priming experiments of guinea pig skin are studied.As a result show, PU and G-COS-
PU test group Cavia porcelluss trial zone skin has no any irritant reaction without erythema, edema, and each time point mean primary stimulates and refers to
Number is 0 (being shown in Table 2).Illustrate that the dressing of G-COS-PU fibers has no stimulation to testing guinea pig skin.Each test group during test
Animal general status are good (not including local skin situation), Non Apparent Abnormality performance.PU and G-COS-PU test groups and the moon
Property each animal of matched group inducing and skin is showed no the diseases such as erythema, edema at left and right sides abdominal rib portion and depilation during exciting
Shape, excites rear animal skin reaction average rank to be 0, and anaphylaxiss incidence rate is 0%.After excitation 24h and 48h, positive right
There is erythema according to (DNFB) Zu Ge animal unnairings area skin, positive controls anaphylaxiss incidence rate is
100% (being shown in Table 2).
The sensitization of skin experimental result of table 2PU and G-COS-PU fiber accessories
Embodiment 8：
Step 1：With stannous octoate as catalyst, Polyethylene Glycol (3g, Mn=400) cause alkynyl for macromole evocating agent
Lactide monomer (12.0g) body ring-opening polymerisation, stannous octoate consumption is the 0.15mol% of alkynyl glycolide monomer consumption,
Reaction temperature：130 DEG C, the response time：24h.After reaction terminates, crude product chloroform dissolves, dehydrated alcohol precipitation, then
48h is vacuum dried in 40 DEG C, biodegradable polyesters ether of the side chain containing alkynyl is obtained.
Step 2：Weigh biodegradable polyesters ether of the 2.0g step 1 gained side chain containing alkynyl to be dissolved in chloroform and be placed in
In four-hole boiling flask, lead to nitrogen, and be heated to 100 DEG C；The dicyclohexyl diisocyanate of 1.2g is subsequently adding, is reacted at 90 DEG C
Performed polymer is obtained after 5h；Finally, the chain extender BDO and appropriate catalyst dibutyltin dilaurylate of 0.7g are added,
Continue to react 3h at 90 DEG C.After reaction terminates, crude product is purified to obtain Biodegradable polyurethane of the side chain containing alkynyl.
Step 3：(1) by 3g chitooligosaccharidequaternary quaternary ammonium salt (Mw=2180) be dissolved in deionized water, add a certain amount of 12
Sodium alkyl sulfonate, both mol ratios are 1:5,3h is reacted at room temperature, lyophilization obtains the oligochitosan quaternary ammonium of alkyl sulfonic acid
Salt.(2) above-mentioned gained alkyl sulfonic acid chitooligosaccharidequaternary quaternary ammonium salt is dissolved in into DMF, is added to Methyl benzenesulfonyl
Chlorine, both press 1:9 mol ratio feeds intake, and adds catalyst 4- diamino-pyridines, and catalyst amount is chitooligosaccharidequaternary quaternary ammonium salt matter
The 2.5% of amount, under nitrogen protection 6h, the purified process of product are reacted at 10 DEG C.(3) in N,N-dimethylformamide
In, in molar ratio 1:5 rate of charge adds the solid product and Hydrazoic acid,sodium salt of above-mentioned synthesis, and 5h, reaction knot are reacted at 90 DEG C
Shu Hou, product is purified and is vacuum dried, that is, obtain Azide oligochitosan.
Step 4：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell obtained by step 2 and step 3 difference
Oligosaccharide quaternary ammonium salt is dissolved in tetrahydrofuran, then polymer solution is added in the tetrahydrofuran containing CuBr under nitrogen protection,
Reacting at normal temperature without light 20h, obtains the polyurethane of chitooligosaccharidequaternary quaternary ammonium salt modification.
Step 5：The polyurethane (2.0g) of the chitooligosaccharidequaternary quaternary ammonium salt modification of step 4 gained is dissolved in into tetrahydrofuran and N, N-
(volume ratio is 4 in dimethylformamide solvent pairs:6) the Electrospun solution that mass-volume concentration is 15%, is obtained, through magnetic force
Electrospun liquid supplying device is injected after stirring, ultrasonic disperse, spinning is carried out under the electrostatic pressure of 15kV, finally obtain oligochitosan season
The polyurethane fiber dressing of ammonium salt modification.Equally pure polyurethane (commercially available, purchase) fiber dressing is built using electrostatic spinning technique.
Fig. 4 is escherichia coli and staphylococcus glucose coccus in the pure polyurethane fiber dressing (PU) of electrostatic spinning and above-mentioned conjunction
Into chitooligosaccharidequaternary quaternary ammonium salt modification polyurethane fiber dressing (G-COS-PU) surface the scanning electron microscope sticked with proliferative conditions
Photo.Show in figure, it is much little in the escherichia coli of G-COS-PU fiber dressing surfaces and the quantity of staphylococcus glucose coccus
In accordingly in PU fiber dressing surface escherichia coli and staphylococcus glucose coccus.As a result show, apply compared to pure PU fibers
Material, G-COS-PU fiber dressing has the higher ability for suppressing escherichia coli and staphylococcus glucose coccus to grow, in other words,
The bacteriostasis property of G-COS-PU fiber dressing is significantly better than corresponding pure PU fibers dressing.
Embodiment 9：
Step 1：With stannous octoate as catalyst, Polyethylene Glycol (4.5g, Mn=1000) cause alkynes for macromole evocating agent
Base glycolide monomer (16.0g) body ring-opening polymerisation, stannous octoate consumption is alkynyl glycolide monomer consumption
0.15mol%, reaction temperature：110 DEG C, the response time：36h.After reaction terminates, crude product chloroform dissolves, anhydrous second
Alcohol is precipitated, and is then vacuum dried 48h in 40 DEG C, obtains biodegradable polyesters ether of the side chain containing alkynyl.
Step 2：Weigh biodegradable polyesters ether of the 2.0g step 1 gained side chain containing alkynyl to be dissolved in chloroform and be placed in
In four-hole boiling flask, lead to nitrogen, and be heated to 100 DEG C；The toluene di-isocyanate(TDI) of 1.2g is subsequently adding, at 100 DEG C 8h is reacted
Performed polymer is obtained afterwards；Finally, the chain extender BDO and appropriate catalyst dibutyltin dilaurylate of 0.9g are added,
Continue to react 4h at 100 DEG C.After reaction terminates, crude product is purified to obtain Biodegradable polyurethane of the side chain containing alkynyl.
Step 3：(1) by 2.5g chitooligosaccharidequaternary quaternary ammonium salt (Mw=4805) be dissolved in deionized water, add a certain amount of ten
Dialkyl sulfonates, both mol ratios are 1:4,2h is reacted at room temperature, lyophilization obtains the oligochitosan season of alkyl sulfonic acid
Ammonium salt.(2) above-mentioned gained alkyl sulfonic acid chitooligosaccharidequaternary quaternary ammonium salt is dissolved in into DMF, is added to Methyl benzenesulfonyl
Chlorine, both press 1:6 mol ratio feeds intake, and adds catalyst 4- diamino-pyridines, and catalyst amount is chitooligosaccharidequaternary quaternary ammonium salt matter
The 2.5% of amount, under nitrogen protection 10h, the purified process of product are reacted at 0 DEG C.(3) in N,N-dimethylformamide
In, in molar ratio 1:4 rate of charge adds the solid product and Hydrazoic acid,sodium salt of above-mentioned synthesis, and 5h, reaction knot are reacted at 90 DEG C
Shu Hou, product is purified and is vacuum dried, that is, obtain Azide oligochitosan.
Step 4：By Biodegradable polyurethane of the side chain containing alkynyl and Azide shell obtained by step 2 and step 3 difference
Oligosaccharide quaternary ammonium salt is dissolved in tetrahydrofuran, polymer solution is added in the tetrahydrofuran containing CuBr under nitrogen protection, room temperature
Lucifuge reacts 24h, obtains the polyurethane of chitooligosaccharidequaternary quaternary ammonium salt modification.
Step 5：The polyurethane (2.0g) of the chitooligosaccharidequaternary quaternary ammonium salt modification of step 4 gained is dissolved in into a certain amount of N, N- bis-
In methylformamide, the Electrospun solution that mass-volume concentration is 15% is obtained, electricity is injected after magnetic agitation, ultrasonic disperse
Spinning liquid supplying device, carries out spinning under the electrostatic pressure of 20kV, finally obtains the polyurethane fiber of chitooligosaccharidequaternary quaternary ammonium salt modification
Dressing.Equally pure polyurethane (commercially available, purchase) fiber dressing is built using electrostatic spinning technique.
With healthy, just adult Albino guinea pig as experimental animal, carry out the dressing of PU fibers and G-COS-PU fiber dressing pair
The influence research of animal wound surface granulation tissue growth, the results are shown in Table 3.Postoperative 4th day, each group wound surface cleaning, surface is without obvious pus
Sexual secretion adheres to, and wound base granulation grows a little, scarlet；Postoperative 8th day, group wound surface cleaning, surface was adhered to without purulent secretion,
Wound base is ruddy, each group wound surface cleaning, granulation raised growth, scarlet graininess, tactile easy bleeding.Each group granulation tissue life in table 3
Into amount data display, G-COS-PU fiber dressing group upper 4 days and 8 days granulation tissue growing amounts are above corresponding PU fibers dressing
Group, shows that the dressing of G-COS-PU fibers is more beneficial for the reparation and healing of wound surface compared to PU fiber dressing.
The impact that table 3PU and G-COS-PU fiber accessories grow to animal wound surface granulation tissue
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of oligochitosan or derivatives thereof modification polyurethane fiber dressing preparation method, it is characterised in that including following step
Suddenly：
Step one：Alkynyl lactide monomers ring-opening polymerisation is caused using Polyethylene Glycol, synthesizes biodegradable of the side chain containing alkynyl
Polyester ether；
Step 2：With biodegradable polyesters ether of the side chain containing alkynyl as soft section, synthesize with diisocyanate and chain extender reaction
Biodegradable polyurethane of the side chain containing alkynyl；
Step 3：Synthesis Azide oligochitosan or derivatives thereof；
Step 4：Side chain Biodegradable polyurethane and Azide oligochitosan containing alkynyl or derivatives thereof generation click chemistry is anti-
Should, synthesize the polyurethane of oligochitosan or derivatives thereof modification；
Step 5：The polyurethane fiber dressing of oligochitosan or derivatives thereof modification is built by electrostatic spinning technique.
2. the preparation method of the polyurethane fiber dressing of oligochitosan according to claim 1 or derivatives thereof modification, it is special
Levy and be：The general structure of alkynyl lactide monomers described in step one is as shown in (I)：
Wherein, R1、R2、R3And R4Identical or different is respectively hydrogen atom, methyl or alkynyl, and R1、R2、R3And R4At least one
Individual is alkynyl.
3. the preparation method of the polyurethane fiber dressing of oligochitosan according to claim 1 or derivatives thereof modification, it is special
Levy and be：In step one, the Polyethylene Glycol is with the molar feed ratio of alkynyl lactide：1:5～1:50；The Polyethylene Glycol
Range of number-average molecular weight be：200～4000；The polymerizing condition of the biodegradable polyesters ether of the synthesis side chain containing alkynyl
For：Catalyst selects stannous octoate, catalyst amount for alkynyl lactide monomers consumption 0.01～0.3mol%, reaction temperature
For 80～150 DEG C, the response time is 6～54h.
4. the preparation method of the polyurethane fiber dressing of oligochitosan according to claim 1 or derivatives thereof modification, it is special
Levy and be：In step 2, the side chain contains the synthesis of the Biodegradable polyurethane of alkynyl, and actual conditions is：
The side chain contains the molar feed ratio of the biodegradable polyesters ether, diisocyanate and chain extender of alkynyl：1:(2
～10):(1～6)；
Described diisocyanate is in hexamethylene diisocyanate, dicyclohexyl diisocyanate and toluene di-isocyanate(TDI)
At least one；
Described chain extender is at least in ethylene glycol, 1,4- butanediols, diglycol, ethylenediamine and 1,4- butanediamine
Kind.
5. the preparation method of the polyurethane fiber dressing of oligochitosan according to claim 1 or derivatives thereof modification, it is special
Levy and be：In step 3, described oligochitosan or derivatives thereof is oligochitosan or chitooligosaccharidequaternary quaternary ammonium salt.
6. the preparation method of the polyurethane fiber dressing of oligochitosan according to claim 1 or derivatives thereof modification, it is special
Levy and be：In step 3, described Azide oligochitosan or derivatives thereof is by oligochitosan or derivatives thereof and Hydrazoic acid,sodium salt
Reaction is prepared, and specifically includes following steps：(1) it is oligochitosan or derivatives thereof is soluble in water, add dodecyl sulphur
Sour sodium, both mol ratios are 1:1～1:10,0.5～8h is reacted at room temperature, lyophilization obtains the oligochitosan of alkyl sulfonic acid
Or derivatives thereof；(2) alkyl sulfonic acid oligochitosan or derivatives thereof is dissolved in into dimethylformamide, is added to Methyl benzenesulfonyl
Chlorine, both mol ratios are 1:1～1:30, add catalyst 4- diamino-pyridines, catalyst amount is oligochitosan or it is derivative
The 0.5～5% of amount of substance, 4～12h is reacted under nitrogen protection in -20-40 DEG C, obtains product；(3) in dimethylformamide,
In molar ratio 1:1～1:50 rate of charge adds the product and Hydrazoic acid,sodium salt of step (2), react 2 in 60～120 DEG C～
12h, after reaction terminates, obtains Azide oligochitosan or derivatives thereof.
7. the preparation method of the polyurethane fiber dressing of oligochitosan according to claim 1 or derivatives thereof modification, it is special
Levy and be：In step 4, Biodegradable polyurethane of the side chain containing alkynyl and Azide oligochitosan or derivatives thereof occur
The concrete operations of click chemistry reaction comprise the steps：Biodegradable polyurethane of the side chain containing alkynyl and Azide shell is few
Sugar or derivatives thereof is dissolved in organic solvent, and both mol ratios are 20:1～1:20；Above-mentioned mixed solution is added to contain and is urged
In the organic solvent of agent, 6～36h of reacting at normal temperature without light obtains the polyurethane of described oligochitosan or derivatives thereof modification.
8. the preparation method of the polyurethane fiber dressing of oligochitosan according to claim 7 or derivatives thereof modification, it is special
Levy and be：Described catalyst is Cu-lyt. or mol ratio is 1:One kind in 1 copper sulfate and ascorbic acid mixture；
The consumption of the catalyst is the 1～20% of Biodegradable polyurethane mole of the side chain containing alkynyl；
Described organic solvent is at least one in tetrahydrofuran, N,N-dimethylformamide and dimethyl sulfoxide.
9. the preparation method of the polyurethane fiber dressing of oligochitosan according to claim 1 or derivatives thereof modification, it is special
Levy and be：In step 5, the electrostatic spinning technique builds the system of the polyurethane fiber dressing of oligochitosan or derivatives thereof modification
Preparation Method is as follows：The polyurethane that oligochitosan or derivatives thereof is modified is dissolved in organic solvent, mass-volume concentration is obtained for 5
～20% Electrospun solution, carries out spinning under the electrostatic pressure of 10～30kV.
10. the polyurethane fiber dressing of a kind of oligochitosan or derivatives thereof modification, it is characterised in that according to claim 1～9 times
Preparation method described in one is obtained.
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