CN101486774A - Quaternised chitosan-polycaprolactone grafting copolymer, preparation, reticulate membrann prepared by the copolymer and method for preparing the copolymer - Google Patents
Quaternised chitosan-polycaprolactone grafting copolymer, preparation, reticulate membrann prepared by the copolymer and method for preparing the copolymer Download PDFInfo
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Abstract
The invention discloses a quaternary ammonium chitosan-polycaprolactone grafted copolymer and a preparation method thereof as well as a reticular membrane prepared by the copolymer and a method thereof, wherein, the polycaprolactone branched chain of the uaternary ammonium chitosan-polycaprolactone grafted copolymer is grafted on the chitosan C-6 position, the 2-hydroxy-3-methyl amine propyl chloride side chain is connected to the chitosan C-2-position, and the obtained grafted copolymer material is loaded with selected drugs by a method of solution mixing and assembled into a gradient-structured reticular membrane by using the electro-wet spinning technology. The membrane has the advantages of good mechanical properties, adjustable pore structure, bio-degradability, moisture retention and air permeability, anti-bacterial and bactericidal capacity and drug controlled release capacity. The process of material synthesizing and processing and preparation for the membrane is simple, the grafted copolymer material structure and the membrane structure are adjustable, the drug release rate is controllable, and the adopted raw materials are mainly natural biological material and have rich sources. The membrane can be used in the treatment of different degrees of skin injury and in the tissue engineering scaffolds for follow-up skin tissue repair.
Description
Technical field
The present invention relates to functional high molecule material and field of tissue engineering technology.。
Technical background
Chitosan is a kind of linear macromolecule polysaccharide that is coupled together by β-1,4 glycosidic link by glucosamine, its chemistry β by name-(1,4)-2-amino-DDG.Chitosan mainly is to handle chitin by concentrated base to obtain.Chitosan has good biocompatibility as a kind of natural biological polymer, can be by biological degradation, and degraded product does not have toxicity.In addition, chitosan also has unique character such as antibacterium, microbial resistance, cellular affinity, promotion wound healing.Therefore, it is widely used in fields such as medicine, biotechnology, chemical engineering and organizational project.The subject matter that chitosan faces in application is that the mechanical property under hygrometric state is very poor, the stability that poroid film of chitosan or fibrous web-like film all are difficult to keep basic mechanical performance under hydration status and keep its morphological structure.New research is pointed out, chitosan-caprolactone grafting copolymer fibrous web-like film (Ying Wan, Hua Wu, BoXiao, Xiaoying Cao, Siqin Dalai, Polymers for Advanced Technologies, 2009, in the printing, DOI:10.1002/pat.1332) under hygrometric state, have enough good mechanical strength and have certain germ resistance and better surface reaction activity.Therefore, consider that from mechanical property, germ resistance and surface properties this fibrid reticular membrane is applicable to wound treatment and skin tissue engineering scaffold.
Antibiotic and the anti-microbial properties of chitosan itself has obtained extensive studies.Result of study points out that the anti-microbial property of chitosan comes from (1) chitosan chain-NH
2The positive charge of group combines with the negative charge of cell surface liposome, suppresses the mobility of cell, thereby suppresses the growth of bacterium; (2) chitosan of oligomer can pass cell walls and enter in the cell, suppresses the formation of mRNA in the born of the same parents, thereby suppresses the growth of bacterium.Since contain on the chitosan skeleton be easy to other organo-functional group reaction-NH
2,-OH group, different chitosan derivatives has also obtained extensive studies.
Compare n-trimethyl chitosan chloride (trimethylammonium chitosan, Zhi shen Jia, Dongfeng shen, Weil iang Xu, Carbohydrate research 2001,333:1 with the chitosan that does not carry out any chemical modification; The diethylmethyl chitosan, M.R.Avadi, A.M.M.Sadeghi, A.Tahzibi, Kh.Bayati, M.Pouladzadeh, M.J.Zohuriaan-Mehr, M.Rafiee-Tehrani.European Polymer.Journal 2004 40:1355) owing to have the quaternized side chain of strong positive charge, has intensive sterilization more and absorption microbial function.Yet n-trimethyl chitosan chloride is water-soluble or the height swollen, and is difficult to be prepared into the cross filament reticular membrane of excellent property.
Except the antibiotic and anti-microbial properties of material itself, suitable materials processing become the fibrous web-like film and make it to have gradient-structure and have ventilative, preserve moisture, adjustable release pharmic function and suitable degradation rate also will directly and significantly influence the result of wound treatment speed and effect and follow-up skin tissue recovering.
Summary of the invention
The technology of preparing that the objective of the invention is to address the above problem and a kind of n-trimethyl chitosan chloride-polycaprolactone grafting copolymer preparation method is provided and is processed into the gradient-structure reticular membrane.Chitosan being carried out mechanics enhancing and antibiotic and sterilizing performance enhanced while, the new grafting copolymer of synthetic is processed into the reticular membrane that loads medicine and have specific modality by grafting polycaprolactone side chain and quaternized modified side chain.The speed may command of medicine can be regulated, be discharged to the degradation rate of this reticular membrane.
Technical scheme of the present invention is:
A kind of n-trimethyl chitosan chloride-polycaprolactone grafting copolymer, this polycaprolactone side chain grafting is on chitosan C-6 position, 2-hydroxyl-3-first ammonium propyl chloride (N-[(2-hydroxy-3-trimethylammonium) propyl] chloride, be abbreviated as HTPC) side chain is connected on the chitosan C-2 position.
Preferably, polycaprolactone substitution in side chain degree is 5-25%, and the weight content that the polycaprolactone side chain accounts for grafting copolymer is 21-55wt%; The substitution value of HTPC side chain is 27-86%.
The preparation method of this n-trimethyl chitosan chloride-polycaprolactone grafting copolymer is: (1) is 5 * 10 with molecular weight
4～6 * 10
5, deacetylation adds in the dimethyl formamide greater than 96% chitosan powder, presses in the chitosan unit-NH
2With the Tetra hydro Phthalic anhydride mol ratio be that 1:2～1:3 feeds intake in 100～120 ℃ of reaction 8～12h, reaction product is precipitated in ethanol after removing reaction medium, collecting precipitation water, ethanol wash respectively and drying after be prepared into the phthalyl chitosan;
(2) phthalyl chitosan and caprolactone are added in the toluene under nitrogen protection in 100～120 ℃ of copolymerization 24～36h by weight 1:1～1:5, prepare the phthalyl chitosan-polycaprolactone grafting copolymer;
(3) the phthalyl chitosan-polycaprolactone grafting copolymer is removed behind the homopolymer with acetone be processed into fine powder with the liquid nitrogen mill, this grafting copolymer obtains chitosan-polycaprolactone grafting copolymer in 90～120 ℃ through the hydrazine hydrate protection that deaminizes under nitrogen protection;
(4) with chitosan-polycaprolactone grafting copolymer fine powder and Racemic glycidol Trimethylamine 99 chlorine (glycidyltrimethylammonium chloride) in molar ratio 1:1～1:4 at aqueous phase in 70～90 ℃ of reaction 12～18h, handle also through 5 times of cold acetones (ice-water bath) and hot ethanol extraction (soxhlet's extractor) then and obtain n-trimethyl chitosan chloride-polycaprolactone grafting copolymer after the drying to reaction volume.
Further, the reticular membrane of described n-trimethyl chitosan chloride-polycaprolactone grafting copolymer preparation has gradient-structure, the end face of film is that micropore (pore diameter range 2-40 μ m) form, bottom surface are macropore (pore diameter range 110-250 μ m) form, and each layer is linked as integral body naturally in assembling process.
Further, the preparation method of described n-trimethyl chitosan chloride-polycaprolactone grafting copolymer reticular membrane is in 0.5～1.0% the acetic acid solution for n-trimethyl chitosan chloride-polycaprolactone grafting copolymer being dissolved in concentration, the Sulfadiazine Silver that adds 3～5wt% in solution utilizes ultrasonic refiner to be prepared into the grafting copolymer solution that concentration is 1～2.5wt%; Utilize electricity-wet spinning technology that grafting copolymer solution is spun into the micrometer fibers reticular membrane.
Further, the n-trimethyl chitosan chloride of described loading medicine-polycaprolactone grafting copolymer reticular membrane, it is characterized in that: with antibiotic or germ killing drugs before reticular membrane machine-shaping with n-trimethyl chitosan chloride-abundant mixing of polycaprolactone grafting copolymer solution, make electricity consumption-wet spinning technology and be processed into layered gradient structure reticular membrane from the mixing solutions that the distance of liquid level will load medicine by control precipitated liquid concentration or regulation and control sample reception dish.The end face of film is that micropore (pore diameter range 2～40 μ m) form, bottom surface are macropore (pore diameter range 110～250 μ m) form, and each layer is linked as integral body naturally in assembling process.
The concrete preparation method of the n-trimethyl chitosan chloride of above-mentioned medicine carrying thing-polycaprolactone grafting copolymer gradient-structure reticular membrane is as follows:
N-trimethyl chitosan chloride-polycaprolactone grafting copolymer powder is dissolved in acetic acid aqueous solution, utilize refiner to be prepared into uniform strong solution after in solution, adding pharmaceutical, move to after the degasification in the take-up reel that under the high voltage direct current electro ultrafiltration, sprays into continuously in the jet pipe of electricity-wet spinning equipment in the settling tank and build up the gradient-structure reticular membrane.Taking-up is respectively embathed 8h with 70% and 80% ethanol with reticular membrane respectively film is deposited 8h in settling tank after, spends the night with 99.5% alcohol immersion again, immerses the Na of 5M after the dry air
2CO
3Solution 3h is washed till neutrality with distilled water, dry air final vacuum drying.
Wherein, acetate water dissolution concentration is 0.5～1.0%; The concentration of n-trimethyl chitosan chloride-polycaprolactone grafting copolymer solution is 1～2.5wt%; The medicine that loads is a Sulfadiazine Silver, and heap(ed) capacity is 3～5wt%; The distance of spout and settling tank liquid level is 5～20cm, and the volts DS between spout and the settling tank ground wire is 5～15 kilovolts; Precipitated liquid is 60～70% ethanol in the settling tank; Sample reception dish mobile range is 0～15cm in the settling tank; Average fibre diameter is 2.2～9 μ m; Reticular membrane thickness is 500 μ m～3mm, and the reticular membrane planar dimension is determined by sample reception dish size; Reticular membrane has gradient-structure, and end face is that micropore form (pore diameter range 2～40 μ m), bottom surface are big pore morphology (pore diameter range 110～250 μ m).The final content of Sulfadiazine Silver in reticular membrane is 0.04～0.12mg/cm
2
Advantage of the present invention is: by the grafting copolymer good mechanical performance of chitosan and caprolactone grafting copolymerization gained; By the further quaternized gained material of chitosan-polycaprolactone being had better processability energy and good anti-microbial property; Has the antibiotic and bactericidal property of high ventilation and moisture retention and enhanced by the n-trimethyl chitosan chloride-polycaprolactone grafting copolymer gradient-structure reticular membrane that loads the Sulfadiazine Silver gained; The fiber surface wetting ability is strong; The degradation rate of reticular membrane can be regulated; Drug release rate may command in the reticular membrane.
Description of drawings
Fig. 1 is the chemical structural formula of n-trimethyl chitosan chloride-polycaprolactone grafting copolymer.
Embodiment
Below in conjunction with accompanying drawing technical scheme of the present invention is further described in detail.
With molecular weight is 5.2 * 10
5, deacetylation is that 96.4% 10g chitosan powder is dispersed in the 200ml dimethyl formamide, the 27.6g Tetra hydro Phthalic anhydride is added, in 120 ℃ of reaction 8h.Add the 500ml dehydrated alcohol after removing Tetra hydro Phthalic anhydride, be prepared into the phthalyl chitosan of 100% amido protecting after collected throw out water, the washing with alcohol drying.
2.0g phthalyl chitosan handled in reactor with high pure nitrogen add 2.0g caprolactone and 4ml toluene behind the 30min, add the stannous 2-ethylhexoate that is equivalent to caprolactone monomer 1mol% in addition, nitrogen protection was reacted 24 hours for following 100 ℃.Reaction product obtains the phthalyl chitosan-polycaprolactone grafting copolymer after soxhlet's extractor is with acetone extract 24h.2.0g phthalyl chitosan-polycaprolactone grafting copolymer is dispersed in the 20ml dimethyl formamide; add the 4ml hydrazine hydrate in 100 ℃ of reaction 2h; throw out water, ethanol are prepared into the chitosan-polycaprolactone grafting copolymer 1.41g that deaminizes fully and protect, polycaprolactone content 26.7wt% after washing drying respectively.Fig. 1 seen in the chemical structural formula of n-trimethyl chitosan chloride-polycaprolactone grafting copolymer.
3.0g chitosan-polycaprolactone grafting copolymer fine powder and 6.6ml Racemic glycidol Trimethylamine 99 chlorine are reacted 12h at the 30ml aqueous phase in 85 ℃, obtain n-trimethyl chitosan chloride-polycaprolactone grafting copolymer 4.36g, quaternized side substitution degree 36.8% after handling with alcohol extraction with 5 times of cold acetones (ice-water bath) precipitations, in soxhlet's extractor to reaction volume.
N-trimethyl chitosan chloride-polycaprolactone grafting copolymer powder is dissolved in 1.0% acetic acid aqueous solution to be prepared into 1.5wt% and to wait to spin solution and add the 4wt% Sulfadiazine Silver, press with bestowing 10 Kilovolt Direct Currents in the jet pipe that is loaded into electricity-wet spinning equipment after the degasification of refiner mixing, medicine carrying solution is sprayed into settling tank and is spun into the gradient-structure reticular membrane.Take out reticular membrane and with 70% and 80% ethanol it is respectively washed 8h respectively, spend the night with 99.5% alcohol immersion again, immerse 5M Na after the dry air
2CO
3Solution 3h is washed till neutrality with distilled water, dry air final vacuum drying.Reticular membrane mean thickness 1647 μ m, planar dimension is 10cm * 10cm, end face mean pore size 27 μ m, bottom surface mean pore size 104 μ m.Average fibre diameter is 5.2 μ m.Reticular membrane drug loading mean value is 0.084mg/cm
3
Its antibiotic and bactericidal property is to measure with spectrographic technique, its concrete steps are: it is 0.23 contain in the golden staphylococci nutrient solution in 37 ℃ of cultured continuously 24h that 10mm * 10mm square sample is immersed the 10mi light absorption value, and the mean value of the light absorption value that records in 6h, 12h, 18h and 24h is respectively 0.17,0.15,0.08 and 0.02; It is 0.21 contain in the intestinal bacteria nutrient solution in 37 ℃ of cultured continuously 24h that 10mm * 10mm square sample is immersed the 10ml light absorption value, and the mean value of the light absorption value that records in 6h, 12h, 18h and 24h is respectively 0.21,0.16,0.11 and 0.08.
With diameter is the 1.5cm sample, immerses in the 10ml phosphate buffer soln (PBS), discharges medicine in 37 ℃ in shaking incubator.50wt% and 100wt% burst size time corresponding are about 6 days (mean value) and 22 (mean values) sky respectively.
Confirm that from the said determination method n-trimethyl chitosan chloride-polycaprolactone grafting copolymer gradient-structure reticular membrane has the antibiotic and germicidal action of highly significant to golden staphylococci or intestinal bacteria.
With molecular weight is 5.2 * 10
5, deacetylation is that 96.4% 10g chitosan powder and 18.4g Tetra hydro Phthalic anhydride react in the 200ml dimethyl formamide, is prepared into the phthalyl chitosan of 100% amido protecting through the method identical with embodiment one.
2.0g phthalyl chitosan is handled adding 4.0g caprolactone and 6ml toluene behind the 30min with high pure nitrogen in reactor, add the stannous 2-ethylhexoate that is equivalent to caprolactone monomer 1mol% in addition, prepare chitosan-polycaprolactone grafting copolymer 1.63g, polycaprolactone content 34.6wt% through the method identical with embodiment one.
3.0g chitosan-polycaprolactone grafting copolymer fine powder and 8.5ml Racemic glycidol Trimethylamine 99 chlorine are joined the 35ml aqueous phase obtain n-trimethyl chitosan chloride-polycaprolactone grafting copolymer 4.87g, quaternized side substitution degree 57.4% through the method identical with embodiment one.Fig. 1 seen in the chemical structural formula of its n-trimethyl chitosan chloride-polycaprolactone grafting copolymer.
N-trimethyl chitosan chloride-polycaprolactone grafting copolymer powder is dissolved in 0.8% acetic acid aqueous solution to be prepared into 1.5wt% and to wait to spin solution and add the 5wt% Sulfadiazine Silver, press with bestowing 10 Kilovolt Direct Currents in the jet pipe that is loaded into electricity-wet spinning equipment after the degasification of refiner mixing, obtain the gradient-structure reticular membrane through the method identical with embodiment one.Reticular membrane mean thickness 1976 μ m, planar dimension is 10cm * 8cm, end face mean pore size 21 μ m, bottom surface mean pore size 117 μ m.Average fibre diameter is 4.3 μ m.Reticular membrane drug loading mean value is 0.11mg/cm
2
Its antibiotic and bactericidal property is to measure with spectrographic technique, its concrete steps are: it is 0.27 contain in the golden staphylococci nutrient solution in 37 ℃ of cultured continuously 24h that 10mm * 10mm square sample is immersed the 10ml light absorption value, and the mean value of the light absorption value that records in 6h, 12h, 18h and 24h is respectively 0.14,0.09,0.06 and 0.02; It is 0.25 contain in the intestinal bacteria nutrient solution in 37 ℃ of cultured continuously 24h that 10mm * 10mm square sample is immersed the 10ml light absorption value, and the mean value of the light absorption value that records in 6h, 12h, 18h and 24h is respectively 0.19,0.14,0.08 and 0.06.
With diameter is the 1.5cm sample, immerses in the 10ml phosphate buffer soln (PBS), discharges medicine in 37 ℃ in shaking incubator.50wt% and 100wt% burst size time corresponding are about 5 days (mean value) and 28 (mean values) sky respectively.
Confirm that from the said determination method n-trimethyl chitosan chloride-polycaprolactone grafting copolymer gradient-structure reticular membrane has the antibiotic and germicidal action of highly significant to golden staphylococci or intestinal bacteria.
With molecular weight is 5.2 * 10
5, deacetylation is that 96.4% 10g chitosan powder and 23g Tetra hydro Phthalic anhydride react in the 200ml dimethyl formamide, is prepared into the phthalyl chitosan of 100% amido protecting through the method identical with embodiment one.
2.0g phthalyl chitosan is handled adding 4.0g caprolactone and 6ml toluene behind the 30min with high pure nitrogen in reactor, add the stannous 2-ethylhexoate that is equivalent to caprolactone monomer 1mol% in addition, prepare chitosan-polycaprolactone grafting copolymer 1.58g, polycaprolactone content 33.7wt% through the method identical with embodiment one.
3.0g chitosan-polycaprolactone grafting copolymer fine powder and 10ml Racemic glycidol Trimethylamine 99 chlorine are joined the 40ml aqueous phase obtain n-trimethyl chitosan chloride-polycaprolactone grafting copolymer 5.36g, quaternized side substitution degree 67.2% through the method identical with embodiment one.Fig. 1 seen in the chemical structural formula of its n-trimethyl chitosan chloride-polycaprolactone grafting copolymer.
N-trimethyl chitosan chloride-polycaprolactone grafting copolymer powder is dissolved in 0.5% acetic acid aqueous solution to be prepared into 1.5wt% and to wait to spin solution and add the 3wt% Sulfadiazine Silver, press with bestowing 15 Kilovolt Direct Currents in the jet pipe that is loaded into electricity-wet spinning equipment after the degasification of refiner mixing, obtain the gradient-structure reticular membrane through the method identical with embodiment one.Reticular membrane mean thickness 2141 μ m, planar dimension is 8cm * 8cm, end face mean pore size 31 μ m, bottom surface mean pore size 117 μ m.Average fibre diameter is 6.1 μ m.Reticular membrane drug loading mean value is 0.54mg/cm
2
Its antibiotic and bactericidal property is to measure with spectrographic technique, its concrete steps are: it is 0.24 contain in the golden staphylococci nutrient solution in 37 ℃ of cultured continuously 24h that 10mm * 10mm square sample is immersed the 10m1 light absorption value, and the mean value of the light absorption value that records in 6h, 12h, 18h and 24h is respectively 0.21,0.15,0.09 and 0.04; It is 0.26 contain in the intestinal bacteria nutrient solution in 37 ℃ of cultured continuously 24h that 10mm * 10mm square sample is immersed the 10ml light absorption value, and the mean value of the light absorption value that records in 6h, 12h, 18h and 24h is respectively 0.22,0.19,0.14 and 0.09.
With diameter is the 1.5cm sample, immerses in the 10ml phosphate buffer soln (PBS), discharges medicine in 37 ℃ in shaking incubator.50wt% and 100wt% burst size time corresponding are about 3 days (mean value) and 19 days (mean value) respectively.
Confirm that from the said determination method n-trimethyl chitosan chloride-polycaprolactone grafting copolymer gradient-structure reticular membrane has the antibiotic and germicidal action of highly significant to golden staphylococci or intestinal bacteria.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (6)
1. n-trimethyl chitosan chloride-polycaprolactone grafting copolymer, it is characterized in that, the grafting of polycaprolactone side chain is on chitosan C-6 position, 2-hydroxyl-3-first ammonium propyl chloride (N-[(2-hydroxy-3-trimethylammonium) propyl] chloride, be abbreviated as HTPC) side chain is connected on the chitosan C-2 position.
2. n-trimethyl chitosan chloride-polycaprolactone grafting copolymer according to claim 1 is characterized in that, polycaprolactone substitution in side chain degree is 5-25%, and the weight content that the polycaprolactone side chain accounts for grafting copolymer is 21-55wt%; The substitution value of HTPC side chain is 27-86%.
3. the synthetic method of the described n-trimethyl chitosan chloride-polycaprolactone grafting copolymer of claim 1 is characterized in that may further comprise the steps:
(1) be 5 * 10 with molecular weight
4～6 * 10
5, deacetylation adds in the dimethyl formamide greater than 96% chitosan powder, presses in the chitosan unit-NH
2With the Tetra hydro Phthalic anhydride mol ratio be that 1:2～1:3 feeds intake in 100～120 ℃ of reaction 8～12h, reaction product is precipitated in ethanol after removing reaction medium, collecting precipitation water, ethanol wash respectively and drying after be prepared into the phthalyl chitosan;
(2) phthalyl chitosan and caprolactone are added in the toluene under nitrogen protection in 100～120 ℃ of copolymerization 24～36h by weight 1:1～1:5, prepare the phthalyl chitosan-polycaprolactone grafting copolymer;
(3) the phthalyl chitosan-polycaprolactone grafting copolymer is removed behind the homopolymer with acetone be processed into fine powder with the liquid nitrogen mill, this grafting copolymer obtains chitosan-polycaprolactone grafting copolymer in 90～120 ℃ through the hydrazine hydrate protection that deaminizes under nitrogen protection;
(4) with chitosan-polycaprolactone grafting copolymer fine powder and Racemic glycidol Trimethylamine 99 chlorine (glycidyltrimethylammonium chloride) in molar ratio 1:1～1:4 at aqueous phase in 70～90 ℃ of reaction 12～18h, handle also through 5 times of cold acetones (ice-water bath) and hot ethanol extraction (soxhlet's extractor) then and obtain n-trimethyl chitosan chloride-polycaprolactone grafting copolymer after the drying to reaction volume.
4. reticular membrane with the preparation of the described n-trimethyl chitosan chloride of claim 1-polycaprolactone grafting copolymer, it is characterized in that, described reticular membrane has gradient-structure, the end face of film is that micropore (pore diameter range 2-40 μ m) form, bottom surface are macropore (pore diameter range 110-250 μ m) form, and each layer is linked as integral body naturally in assembling process.
5. the preparation method of the described n-trimethyl chitosan chloride of claim 4-polycaprolactone grafting copolymer reticular membrane, it is characterized in that, it is in 0.5～1.0% the acetic acid solution that n-trimethyl chitosan chloride-polycaprolactone grafting copolymer is dissolved in concentration, the Sulfadiazine Silver that adds 3～5wt% in solution utilizes ultrasonic refiner to be prepared into the grafting copolymer solution that concentration is 1～2.5wt%; Utilize electricity-wet spinning technology that grafting copolymer solution is spun into the micrometer fibers reticular membrane.
6. according to the n-trimethyl chitosan chloride-polycaprolactone grafting copolymer reticular membrane of any described loading medicine in the claim 3 to 5, it is characterized in that: with antibiotic or germ killing drugs before reticular membrane machine-shaping with n-trimethyl chitosan chloride-abundant mixing of polycaprolactone grafting copolymer solution, make electricity consumption-wet spinning technology and be processed into layered gradient structure reticular membrane from the mixing solutions that the distance of liquid level will load medicine by control precipitated liquid concentration or regulation and control sample reception dish.The end face of film is that micropore (pore diameter range 2～40 μ m) form, bottom surface are macropore (pore diameter range 110～250 μ m) form, and each layer is linked as integral body naturally in assembling process.
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| CN108559009A (en) * | 2017-09-26 | 2018-09-21 | 西南石油大学 | A kind of preparation method of phthaloyl chitosan |
| CN111662457A (en) * | 2020-06-09 | 2020-09-15 | 四川大学 | Polylactic acid grafted quaternized chitosan material, stereo composite crystal nanofiber membrane thereof, and preparation methods and applications of polylactic acid grafted quaternized chitosan material and stereo composite crystal nanofiber membrane |
| CN111662457B (en) * | 2020-06-09 | 2022-07-12 | 四川大学 | Polylactic acid grafted quaternized chitosan material, stereocomplex crystal nanofiber membrane thereof, and preparation methods and applications of polylactic acid grafted quaternized chitosan material and stereocomplex crystal nanofiber membrane |
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