CN118217438A - Chitin/chitosan-based surgical suture and preparation method of functional chitin/chitosan-based surgical suture - Google Patents
Chitin/chitosan-based surgical suture and preparation method of functional chitin/chitosan-based surgical suture Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 223
- 229920002101 Chitin Polymers 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 39
- 239000000835 fiber Substances 0.000 claims abstract description 23
- 230000001112 coagulating effect Effects 0.000 claims abstract description 19
- 230000001954 sterilising effect Effects 0.000 claims abstract description 4
- 230000001172 regenerating effect Effects 0.000 claims abstract description 3
- 238000007493 shaping process Methods 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 134
- 239000000243 solution Substances 0.000 claims description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000007864 aqueous solution Substances 0.000 claims description 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- 230000015271 coagulation Effects 0.000 claims description 18
- 238000005345 coagulation Methods 0.000 claims description 18
- 238000002166 wet spinning Methods 0.000 claims description 17
- 230000006196 deacetylation Effects 0.000 claims description 15
- 238000003381 deacetylation reaction Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 239000011550 stock solution Substances 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 8
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 239000013538 functional additive Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
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- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
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- 229920005615 natural polymer Polymers 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 23
- 239000002994 raw material Substances 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- 238000001816 cooling Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011736 potassium bicarbonate Substances 0.000 description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WFAJBYGUONQMCI-UHFFFAOYSA-N acetic acid urea Chemical compound NC(=O)N.NC(=O)N.NC(=O)N.NC(=O)N.NC(=O)N.NC(=O)N.C(C)(=O)O WFAJBYGUONQMCI-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000238366 Cephalopoda Species 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- RBYVERBYFHDDGV-UHFFFAOYSA-L NC(=O)N.[OH-].[K+].[OH-].[Li+] Chemical compound NC(=O)N.[OH-].[K+].[OH-].[Li+] RBYVERBYFHDDGV-UHFFFAOYSA-L 0.000 description 1
- GPKSRYBYOMDXQM-UHFFFAOYSA-M NC(=O)N.[OH-].[Li+] Chemical compound NC(=O)N.[OH-].[Li+] GPKSRYBYOMDXQM-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- DLKSDVVEGFXDQU-UHFFFAOYSA-N azane;carbonic acid;urea Chemical compound N.NC(N)=O.OC(O)=O DLKSDVVEGFXDQU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical group C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000002439 hemostatic effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- ZWYNGBGVHKVISN-UHFFFAOYSA-L lithium sodium urea dihydroxide Chemical compound NC(=O)N.[OH-].[Li+].[OH-].[Na+] ZWYNGBGVHKVISN-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- VBJNVMKVMZUFLD-UHFFFAOYSA-M potassium;hydrogen carbonate;urea Chemical compound [K+].NC(N)=O.OC([O-])=O VBJNVMKVMZUFLD-UHFFFAOYSA-M 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical class [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XGBOQPVRRBPDDF-UHFFFAOYSA-M sodium;urea;hydroxide Chemical compound [OH-].[Na+].NC(N)=O XGBOQPVRRBPDDF-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
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Landscapes
- Artificial Filaments (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to the technical field of natural polymers and polymer materials, in particular to a chitin/chitosan-based surgical suture and a preparation method of a functional chitin/chitosan-based surgical suture, which comprises the following steps: obtaining a mixture of chitin and aqueous alkali or a mixture of chitosan and aqueous alkali; preparing chitin spinning solution or chitosan spinning solution from the mixture; spinning the chitin spinning solution or the chitosan spinning solution, and then regenerating in a coagulating bath to obtain chitin or chitosan fibers; performing back draft, combining and twisting treatment on chitin or chitosan fiber to obtain yarn; shaping, balancing and sterilizing to obtain the suture line. The invention provides a novel dissolving method for dissolving chitosan and a method for spinning chitosan surgical suture. The method of the invention can not only improve the dissolution rate of chitosan and obtain high-quality high-concentration chitosan spinning solution, thereby providing possibility for industrial production.
Description
Technical Field
The invention relates to the technical field of natural polymers and polymer materials, in particular to a chitin/chitosan-based surgical suture and a preparation method of a functional chitin/chitosan-based surgical suture.
Background
Surgical sutures are a commonly used medical material in surgical procedures for suturing wounds, connective tissue, and are also the most common material implantable into the human body. Surgical sutures are classified into absorbable sutures and non-absorbable sutures according to biodegradability; according to the raw materials, natural polymer-based sutures, synthetic material sutures, and metal sutures are classified.
Chitin is the second largest natural polymer with a content inferior to that of cellulose in nature. Widely exists in the waste of aquatic products such as shrimp and crab shells, squid bones and the like. Chitin can be converted to chitosan by biological or chemical means. When the deacetylation degree of the chitin is more than 50-55%, the chitin is converted into chitosan. The chitin/chitosan has good biocompatibility, degradability and excellent antibacterial property, can promote wound healing, has hemostatic effect, and has wide application in the biomedical field.
Chitin/chitosan contains a large number of intermolecular and intramolecular hydrogen bonds, making it impossible to melt process, and is also difficult to dissolve in water and most organic reagents. Although chitosan can be dissolved in part of acid solvent, chitosan is unstable in acid, and the mechanical property of the material prepared by the chitosan acid solution is poor. In recent years, researchers have developed a variety of new solvent systems for chitin and chitosan, such as aqueous alkali systems, ionic liquids, and the like. The most common chitosan solvent system is alkaline solution, and a great deal of research is being conducted. Chitosan with a degree of deacetylation of more than 60% can be dissolved in a combination of lithium hydroxide-sodium hydroxide-urea (patent 201110099176.3), a combination of lithium hydroxide-potassium hydroxide-urea (patent 201310405191.5), a combination of sodium hydroxide-urea (j. Appl. Polym. Sci.,2014,131 (3), 1082-1090.), a combination of lithium hydroxide-urea (carbohydrate. Polym,2009,78,66-71), but these solvents often require one or even more freeze-thaw cycles to dissolve chitosan, resulting in a large energy consumption, and lithium ions are biotoxic and expensive. KOH, although it can dissolve chitosan without freeze thawing, still needs to be dissolved at low temperatures (Huang J., et al, advanced Functional Materials 2017,27,1701100), resulting in high cost and high energy consumption. Therefore, the problem of low-temperature dissolution cost and energy consumption can be remarkably reduced by increasing the dissolution temperature of chitosan, so that industrial production is possible.
Chitin has biological inertia, and the suture line of chitin is not easy to cause complications or tissue reaction after being implanted into human body, but the mechanical strength of the suture line of chitin is often lower. Chitosan is a deacetylated chitosan product, has excellent antibacterial property, can endow the suture with excellent antibacterial property without adding additional antibacterial agents, and has slightly higher mechanical properties than chitin suture. The chitosan surgical suture disclosed at present mostly uses acetic acid as a dissolution system, and the mechanical property is often poor (patent CN 03129976.6). The chitosan surgical suture disclosed in the patent application number 201010218130.4 and the manufacturing process thereof are that the chitosan surgical suture is prepared by a method of firstly cutting strips and then drawing wires, the suture section is not regular enough, the friction resistance in the use process can be increased, and the inconvenience is brought to the reagent operation.
The tensile strength of the chitosan surgical suture cannot meet the actual clinical requirements, and the chitosan surgical suture cannot be widely applied clinically.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a chitin/chitosan-based surgical suture; the prepared chitin/chitosan surgical suture has high strength, simple and convenient process, safe and environment-friendly solvent and suitability for mass production.
The second object of the invention is to provide a method for preparing the functional chitin/chitosan-based surgical suture.
The scheme adopted by the invention for achieving one of the purposes is as follows: a method for preparing a chitin/chitosan-based surgical suture, comprising the following steps:
(1) Treating chitin with 20-80 wt% concentration alkali water solution at 60-170 deg.c to obtain mixture of chitin and alkali water solution with deacetylation degree not higher than 50% or mixture of chitosan and alkali water solution with deacetylation degree higher than 50%;
(2) Obtaining chitin spinning solution or chitosan spinning solution by adopting any one of the following methods to the mixture obtained in the step (1);
A1, when the mixture of the chitin with the deacetylation degree not exceeding 50% and the alkaline water solution is obtained in the step (1), reducing the temperature of the mixture to-35-30 ℃, adjusting the alkaline water solution to 5-30 wt% of the alkaline concentration, and adding a stabilizer to obtain chitin spinning stock solution;
A2, when the mixture of chitosan with the deacetylation degree higher than 50% and the alkaline water solution is obtained in the step (1), the temperature of the mixture is reduced to-30 ℃, the alkaline water solution is adjusted to be 2-30wt% of the alkaline concentration, and a stabilizer is added to obtain chitosan spinning stock solution;
A3, when the mixture of chitosan with the deacetylation degree higher than 50% and the aqueous alkali solution is obtained in the step (1), removing the aqueous alkali solution in the mixture in the step (1), and dissolving the obtained solid component by using a weak base aqueous solution to obtain a chitosan spinning stock solution, wherein the weak base is a bicarbonate aqueous solution;
A4, when the mixture of chitosan with the deacetylation degree higher than 50% and the aqueous alkali solution is obtained in the step (1), removing the aqueous alkali solution in the mixture in the step (1), dissolving the obtained solid component by using a dilute acid aqueous solution, adding a proper amount of alkali for neutralization, and stirring to obtain chitosan spinning stock solution;
(3) Spinning the chitin spinning solution or the chitosan spinning solution obtained in the step (2), and then regenerating in a coagulating bath to obtain chitin or chitosan fibers;
(4) Performing post-drawing, combining and twisting treatment on the chitin or chitosan fiber obtained in the step (3) to obtain yarn;
(5) And (3) adopting hot and humid steam to carry out shaping treatment on the single fiber or yarn, putting the single fiber or yarn into a standard atmosphere for balancing and sterilizing to obtain a monofilament suture or a suture with a certain specification.
Preferably, in the step (1), the aqueous alkali solution is a KOH aqueous solution or a NaOH aqueous solution or a mixed solution of KOH and NaOH.
Preferably, in the step (2), the concentration of the chitin or chitosan in the chitin spinning solution or the chitosan spinning solution is 1wt% to 15wt%.
Preferably, in the step (2), the stabilizer is one or more of urea, thiourea and polyvinyl alcohol, and the concentration of the stabilizer in the chitin spinning solution or the chitosan spinning solution is 0-20wt%.
Preferably, the method for adjusting the alkali concentration in the mixture in the step (2) is any one of the following methods: a. adding water to the mixture obtained in the step (1) for dilution so as to reduce the concentration of alkali; b. filtering, washing and drying the mixture in the step (1), and then adding the mixture into an aqueous solution of alkali with target concentration to reduce the concentration of the alkali; c. adjusting the alkali concentration of the mixture in the step (1) to 20-60 wt%, reducing the temperature of the mixed solution to not more than 30 ℃ and standing for a period of time, and adding ice cubes or ice water to dilute the alkali concentration to 5-30 wt%.
Preferably, the weak alkali aqueous solution in the step (2) is a single bicarbonate aqueous solution or a mixture of multiple bicarbonate aqueous solutions, and the concentration of the bicarbonate aqueous solution is not 2-10wt%; the dilute acid is one or a mixture of inorganic acid and organic acid, the concentration of the dilute acid aqueous solution is 1-4wt%, the neutralized alkali is at least one of alkaline hydroxide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal bicarbonate, alkaline earth metal bicarbonate, ammonia water, ammonium carbonate and ammonium bicarbonate, and the concentration of the neutralized alkali is 2-30wt%.
Preferably, in the step (3), the spinning method includes wet spinning and dry-jet wet spinning, and the coagulation bath for spinning is a single coagulation bath or a multi-stage coagulation bath; the coagulating bath is one or a mixture solution of a plurality of water, saline solution and water-soluble low-viscosity organic liquid; the salt is a salt containing monovalent, divalent, trivalent cations or anions; the low viscosity organic liquid of the aqueous soluble is at least one of an alcohol, a ketone, an ester, an amide, and an organosulfide.
Preferably, the salt is at least one of potassium salt, sodium salt, chlorine salt, acetate, sulfate and carbonate; the alcohol is methanol or ethanol, and the ketone is acetone; the ester is ethyl acetate; the amide is dimethyl amide or dimethyl acetamide; the organic sulfide is dimethyl sulfoxide.
Preferably, the obtained spinning solution is subjected to filtration and defoaming treatment before the step (3), and the defoaming modes comprise centrifugal defoaming, vacuum static defoaming and continuous defoaming. The spinning process is to make chitin/chitosan spinning stock solution pass through spinning holes with the aperture of 0.05-0.2 mm under the pressure of 0.1-2 Mpa, and stay in a coagulating bath for 1-200 s to be coagulated into filaments.
Preferably, the coagulating bath temperature for spinning is-10-80 ℃, the water washing temperature is 20-80 ℃, and the draft ratio is 1-2.5.
Preferably, the spinning is performed with a spinneret aperture of 0.08-0.8 mm.
In the preparation process of the chitin/chitosan surgical suture, the chitin/chitosan nascent fiber can be pre-drawn in the coagulating bath, and the multiple coagulating baths play roles of complementary coagulating forming and pre-drawing, so that the coagulating forming of the chitin/chitosan surgical suture fiber is more sufficient, the subsequent drawing is facilitated, and the performance of the fiber is improved.
In the preparation process of the chitin/chitosan surgical suture, the multiple of one draft is limited, and the multiple of two or more drafts can be adopted to improve the draft. The drafting process can comprise multi-stage drafting processes such as hot water, boiling water, steam drafting and the like, and can be mutually alternated with oiling and drying steps, so that the defect of the inside of the fiber caused by excessive drafting is prevented, the compactness of the fiber structure is improved, and the molecules in the fiber are further oriented, so that the mechanical property of the fiber is further improved.
In the preparation process of the chitin/chitosan surgical suture, the solvent in the fiber can be gradually removed by a water washing step by a plurality of water washing processes and the like, so that the internal gaps of the fiber are reduced.
In the preparation process of the chitin/chitosan surgical suture, the drying mode can be a common drying mode, such as hot roller drying and the like.
Preferably, in the preparation process of the chitin/chitosan surgical suture, two or more monofilaments can be twisted into a multi-strand surgical suture on a twisting machine.
The scheme adopted by the invention for achieving the second purpose is as follows: the preparation method of the functional chitin/chitosan-based surgical suture comprises the steps of preparing the chitin/chitosan-based surgical suture by adopting the method, and introducing a cross-linking agent or a functional additive in the preparation process to obtain the functional chitin/chitosan-based surgical suture; the functional additive is added through a spinning dope or coagulation bath.
The functional additive comprises one or more of plasticizer, optical stabilizer, antibacterial agent, surfactant and reinforcing agent.
The invention has the following advantages and beneficial effects:
The invention provides a novel dissolving method for dissolving chitosan and a method for spinning chitosan surgical suture. The method of the invention can not only improve the dissolution rate of chitosan to obtain high-quality high-concentration chitosan spinning solution, but also improve the dissolution temperature of chitosan and reduce the low-temperature dissolution cost and energy consumption, thereby providing possibility for industrial production.
The solution components adopted by the method can be recycled, and the method is safe, environment-friendly, low in cost and suitable for industrial production.
The chitin/chitosan surgical suture prepared by the invention has high strength, simple and convenient process, safe and environment-friendly solvent and suitability for mass production.
The preparation method of the functional chitin/chitosan-based surgical suture provided by the invention can be used for preparing the chitin/chitosan surgical suture with high mechanical property and excellent antibacterial and anti-inflammatory functions, and the surgical suture has degradability without subsequent dismantling.
Drawings
FIG. 1 is a view showing the antibacterial effect of the chitosan surgical suture of example 5;
FIG. 2 is a view showing the antibacterial effect of the chitin surgical suture of example 17;
FIG. 3 is a fluorescent staining chart of the chitosan surgical suture of example 5 after co-culturing with mouse fibroblasts for 72 hours;
Fig. 4 is a view showing the degradation effect of the chitosan surgical suture of example 5.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrative of the present invention, but the contents of the present invention are not limited to the following examples only.
Room temperature conditions are described in the examples below unless otherwise specified.
Example 1
Preparing a KOH solution with the mass fraction of 20wt%, adding chitin raw materials, heating at 60 ℃ for 20 minutes, cooling to 30 ℃, adding water and urea into the mixed solution to enable the mass fraction of KOH in the mixed solution to be 5wt%, the mass fraction of urea to be 2wt%, and the mass fraction of chitin to be 4wt%, stirring to obtain a clear and transparent chitin solution, and centrifuging and defoaming to obtain the transparent chitin solution. The chitin solution is subjected to wet spinning technology to prepare chitin surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And (3) washing the obtained chitin filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitin surgical suture. The tensile strength of the chitin surgical suture is about 180-195 MPa, and the elongation at break is about 12-20%.
Example 2
Preparing a KOH solution with the mass fraction of 40wt%, adding chitin raw materials, heating at 70 ℃ for 20 minutes, cooling to 30 ℃, adding water and urea into the mixed solution to enable the mass fraction of KOH in the mixed solution to be 30wt%, the mass fraction of urea to be 8wt%, and the mass fraction of chitin to be 7wt%, stirring to obtain the chitin solution, and centrifuging and defoaming to obtain the transparent chitin solution. The chitin solution is coagulated into silk by passing through a spinneret orifice with the aperture of 0.2mm under the pressure of 0.2MPa into a saturated potassium carbonate solution with the temperature of 0 ℃, and the coagulating bath process is 100cm. And (3) washing the obtained chitin filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitin surgical suture. The tensile strength of the chitin surgical suture is about 195-225 MPa, and the elongation at break is about 15-24%.
Example 3
Preparing a KOH solution with the mass fraction of 40wt%, adding chitin raw materials, heating at 70 ℃ for 60 minutes, cooling to 30 ℃, adjusting the mass fraction of KOH in the mixed solution to 30wt%, standing at 5 ℃ for 2 hours, adding crushed ice to ensure that the final concentration of KOH is 20wt% and the mass fraction of chitin is 7wt%, stirring to obtain the chitin solution, and centrifuging and defoaming to obtain the transparent chitin solution. The chitin solution is subjected to wet spinning technology to prepare chitin surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And (3) washing the obtained chitin filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitin surgical suture. The tensile strength of the chitin surgical suture is about 200-225 MPa, and the elongation at break is about 13-20%.
Example 5
Preparing a KOH solution with the mass fraction of 60wt%, adding a chitin raw material, heating for 30 minutes at 80 ℃, cooling to 30 ℃, adding water and urea into the mixed solution to enable the mass fraction of KOH in the mixed solution to be 10wt%, the mass fraction of urea to be 2wt%, and the mass fraction of chitosan to be 6wt%, stirring to obtain a clear and transparent chitosan solution, and centrifuging and defoaming to obtain the transparent chitosan solution. The chitosan solution is subjected to wet spinning technology to prepare chitosan surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And (3) washing the obtained chitosan filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 195-205 MPa, and the elongation at break is about 20-35%. As shown in the figure I, the chitosan surgical suture prepared by the method has excellent antibacterial property, cell compatibility and biodegradability.
Example 6
Preparing a KOH solution with the mass fraction of 60wt%, adding a chitin raw material, heating at 80 ℃ for 60 minutes, washing, adding chitosan solid into a KOH-thiourea aqueous solution to enable the mass fraction of KOH in the mixed solution to be 20wt%, the mass fraction of thiourea to be 5wt%, and the mass fraction of chitosan to be 6wt%, stirring to obtain a clear and transparent chitosan solution, and centrifuging and defoaming to obtain the transparent chitosan solution. The chitosan solution is subjected to wet spinning technology to prepare chitosan surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And (3) washing the obtained chitosan filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 192-204 MPa, and the breaking elongation is about 22-35%.
Example 7
Preparing a KOH solution with the mass fraction of 60wt%, adding a chitin raw material, heating at 80 ℃ for 60 minutes, cleaning, adding chitosan solid into a potassium bicarbonate-urea aqueous solution, enabling the mass fraction of potassium bicarbonate in the mixed solution to be 10wt%, the mass fraction of urea to be 16wt%, and the mass fraction of chitosan to be 6wt%, stirring to obtain a clear and transparent chitosan solution, and centrifuging and defoaming to obtain the transparent chitosan solution. The chitosan solution is subjected to wet spinning technology to prepare chitosan surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And (3) washing the obtained chitosan filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 175-195 MPa, and the breaking elongation is about 20-34%.
Example 8
Preparing a KOH solution with the mass fraction of 60wt%, adding a chitin raw material, heating at 80 ℃ for 60 minutes, cleaning, adding chitosan solid into an ammonium bicarbonate-urea aqueous solution, enabling the mass fraction of ammonium bicarbonate in the mixed solution to be 2wt%, the mass fraction of urea to be 16wt%, and the mass fraction of chitosan to be 6wt%, stirring to obtain a clear and transparent chitosan solution, and centrifuging and defoaming to obtain the transparent chitosan solution. The chitosan solution is subjected to wet spinning technology to prepare chitosan surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And (3) washing the obtained chitosan filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 190-205 MPa, and the elongation at break is about 15-25%.
Example 9
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw materials, heating at 80 ℃ for 60 minutes, washing, adding chitosan solid into an acetic acid-urea aqueous solution, adding potassium bicarbonate, continuously stirring to ensure that the mass fraction of acetic acid in the mixed solution is 1wt%, the mass fraction of potassium bicarbonate is 5wt%, the mass fraction of urea is 10wt%, the mass fraction of chitosan is 6wt%, stirring to obtain a clear and transparent chitosan solution, and centrifuging and defoaming to obtain the transparent chitosan solution. The chitosan solution is subjected to wet spinning technology to prepare chitosan surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And (3) washing the obtained chitosan filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 200-225 MPa, and the elongation at break is about 14-20%.
Example 10
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw material, heating at 80 ℃ for 1h, repeating for 3 times, adding chitosan solid into an acetic acid-urea aqueous solution after cleaning, adding potassium bicarbonate and KOH, continuously stirring to enable the mass fraction of acetic acid in the mixed solution to be 2wt%, the mass fraction of potassium bicarbonate to be 5wt%, the mass fraction of potassium hydroxide to be 16wt%, the mass fraction of urea to be 8wt%, the mass fraction of chitosan to be 5wt%, stirring to obtain a clear and transparent chitosan solution, and centrifuging and defoaming to obtain the transparent chitosan solution. The chitosan solution is subjected to a wet spinning process to prepare the chitosan surgical suture. The chitosan solution is coagulated into filaments by passing through spinneret orifices with the aperture of 0.2mm into saturated potassium carbonate solution with the temperature of 0 ℃ under the pressure of 0.2MPa, and the coagulating bath process is 100cm. And (3) washing the obtained chitosan filaments with deionized water at 80 ℃, and oiling and drying to obtain the chitosan surgical suture with high deacetylation degree. The tensile strength of the chitosan surgical suture is about 220-240 MPa, and the elongation at break is about 20-35%.
Example 11
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw materials, heating for 60 minutes at 80 ℃, cooling to 30 ℃, adjusting the mass fraction of KOH in the mixed solution to 30wt%, standing for 1 hour at 5 ℃, adding crushed ice to ensure that the final concentration of KOH is 12wt% and the mass fraction of chitosan is 7wt%, stirring to obtain a chitosan solution, and centrifuging and defoaming to obtain a transparent chitosan solution. The chitosan solution is subjected to wet spinning technology to prepare chitosan surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And (3) washing the obtained chitosan filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 202-220 MPa, and the breaking elongation is about 22-30%.
Example 12
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw materials, heating for 60 minutes at 80 ℃, cooling to 30 ℃, adjusting the mass fraction of KOH in the mixed solution to 30wt%, standing for 1 hour at 5 ℃, adding crushed ice to ensure that the final concentration of KOH is 12wt% and the mass fraction of chitosan is 7wt%, stirring to obtain a chitosan solution, and centrifuging and defoaming to obtain a transparent chitosan solution. The chitosan solution is subjected to wet spinning technology to prepare chitosan surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And then cleaning the obtained chitosan filaments with deionized water at 50 ℃ through a second path of potassium carbonate solution with the concentration of 25wt% at the temperature of 0 ℃ and the draft ratio of 1.1-1.6, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 250-500 MPa, and the elongation at break is about 10-20%.
Example 13
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw materials, heating for 60 minutes at 80 ℃, cooling to 30 ℃, adjusting the mass fraction of KOH in the mixed solution to 30wt%, standing for 1 hour at 5 ℃, adding crushed ice to ensure that the final concentration of KOH is 12wt% and the mass fraction of chitosan is 7wt%, stirring to obtain a chitosan solution, and centrifuging and defoaming to obtain a transparent chitosan solution. The chitosan solution is coagulated into filaments by a saturated sodium sulfide solution with the pore diameter of 0.2mm under the pressure of 0.2MPa, and the coagulating bath process is 100cm. And then passing through a second channel of 20wt% sodium sulfate solution at 65 ℃ to obtain the draft ratio of 1.1-1.6. And (3) washing the obtained chitosan filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 220-450 MPa, and the elongation at break is about 8-14%.
Example 14
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw materials, heating for 60 minutes at 80 ℃, cooling to 30 ℃, adjusting the mass fraction of KOH in the mixed solution to 30wt%, standing for 1 hour at 5 ℃, adding crushed ice to ensure that the final concentration of KOH is 12wt% and the mass fraction of chitosan is 7wt%, stirring to obtain a chitosan solution, and centrifuging and defoaming to obtain a transparent chitosan solution. The chitosan solution is coagulated into filaments by a spinning hole with the aperture of 0.2mm under the pressure of 0.2MPa into a water solution of 50wt% ethanol/10 wt% citric acid/2 wt% sodium citrate at 20 ℃ and the coagulating bath range is 100cm. And then passing through a second alcohol-water mixed solution, wherein the draft ratio is 1.1-1.6. And (3) washing the obtained chitosan filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 220-350 MPa, and the breaking elongation is about 8-14%.
Example 15
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw materials, heating for 60 minutes at 80 ℃, cooling to 30 ℃, adjusting the mass fraction of KOH in the mixed solution to 30wt%, standing for 1 hour at 5 ℃, adding crushed ice to ensure that the final concentration of KOH is 12wt% and the mass fraction of chitosan is 7wt%, stirring to obtain a chitosan solution, and centrifuging and defoaming to obtain a transparent chitosan solution. The chitosan solution is coagulated into filaments by a spinning hole with the aperture of 0.2mm under the pressure of 0.2MPa in 50wt% methanol/10 wt% potassium chloride aqueous solution with the temperature of 15 ℃ and the coagulation bath range of 100cm. And then passing through a second alcohol-water mixed solution, wherein the draft ratio is 1.1-1.6. And (3) washing the obtained chitosan filaments with deionized water at 50 ℃, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 205-305 MPa, and the breaking elongation is about 6-12%.
Example 16
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw materials, heating for 60 minutes at 80 ℃, cooling to 30 ℃, adjusting the mass fraction of KOH in the mixed solution to 30wt%, standing for 1 hour at 5 ℃, adding crushed ice to ensure that the final concentration of KOH is 12wt% and the mass fraction of chitosan is 7wt%, stirring to obtain a chitosan solution, and adding a certain amount of ethylene glycol diglycidyl ether as a cross-linking agent into the obtained solution, wherein the cross-linking ratio is 2:1. Stirring uniformly at a temperature lower than the gelation temperature of the solution, and then centrifugally defoaming, wherein the chitosan solution is subjected to wet spinning process to prepare chitosan surgical suture, and the chitosan solution enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And then cleaning the obtained chemically crosslinked chitosan filaments by using deionized water at 50 ℃ through a second path of potassium carbonate solution with the concentration of 25wt% at the temperature of 0 ℃ and the draft ratio of 1.1-1.6, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 340-520 MPa, and the elongation at break is about 8-12%.
Example 17
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw materials, heating for 60 minutes at 80 ℃, cooling to 30 ℃, adjusting the mass fraction of KOH in the mixed solution to 30wt%, standing for 1 hour at 5 ℃, adding crushed ice to ensure that the final concentration of KOH is 12wt% and the mass fraction of chitosan is 7wt%, stirring to obtain a chitosan solution, and centrifuging and defoaming to obtain a transparent chitosan solution. The chitosan solution is subjected to wet spinning technology to prepare chitosan surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And then cleaning the obtained chitosan filaments with deionized water at 50 ℃ through a second path of potassium carbonate solution with the concentration of 25wt% at the temperature of 0 ℃ and the draft ratio of 1.1-1.6, and oiling and drying to obtain the chitosan surgical suture. The tensile strength of the chitosan surgical suture is about 250-420 MPa, and the breaking elongation is about 12-18%. Under the condition of avoiding light, the obtained chitosan fiber is soaked in silver nitrate aqueous solution with the concentration of 0.01mol/L, after 12 hours, the chitosan fiber is taken out, and silver nano particles are generated in situ by a hydrothermal method at 140 ℃ to obtain the chitin/nano silver composite fiber with the sterilizing effect. As shown in figure 2, the chitin/nano silver composite fiber prepared by the method has relatively excellent broad-spectrum antibacterial property.
Example 18
Preparing a KOH solution with the mass fraction of 60wt%, adding chitin raw materials, heating for 60 minutes at 80 ℃, cooling to 30 ℃, adjusting the mass fraction of KOH in the mixed solution to 30wt%, standing for 1 hour at 5 ℃, adding crushed ice to ensure that the final concentration of KOH is 12wt% and the mass fraction of chitosan is 7wt%, stirring to obtain a chitosan solution, and centrifuging and defoaming to obtain a transparent chitosan solution. The chitosan solution is subjected to wet spinning technology to prepare chitosan surgical suture, and enters into 0 ℃ saturated potassium carbonate solution through a spinneret orifice with the aperture of 0.2mm to be coagulated into filaments under the pressure of 0.2MPa, and the coagulation bath range is 100cm. And then cleaning the obtained chitosan filaments with deionized water at 50 ℃ through a second path of potassium carbonate solution with the concentration of 25wt% at the temperature of 0 ℃ and the draft ratio of 1.1-1.6, and oiling and drying to obtain the chitosan surgical suture. Two or more single chitosan surgical sutures are twisted on a twisting machine to obtain the chitosan multifilament suture, the tensile strength of the chitosan multifilament suture is about 500-800 MPa, and the elongation at break is about 10-20%.
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (10)
1. The preparation method of the chitin/chitosan-based surgical suture is characterized by comprising the following steps:
(1) Treating chitin with 20-80 wt% concentration alkali water solution at 60-170 deg.c to obtain mixture of chitin and alkali water solution with deacetylation degree not higher than 50% or mixture of chitosan and alkali water solution with deacetylation degree higher than 50%;
(2) Obtaining chitin spinning solution or chitosan spinning solution by adopting any one of the following methods to the mixture obtained in the step (1);
A1, when the mixture of the chitin with the deacetylation degree not exceeding 50% and the alkaline water solution is obtained in the step (1), reducing the temperature of the mixture to-35-30 ℃, adjusting the alkaline water solution to 5-30 wt% of the alkaline concentration, and adding a stabilizer to obtain chitin spinning stock solution;
A2, when the mixture of chitosan with the deacetylation degree higher than 50% and the alkaline water solution is obtained in the step (1), the temperature of the mixture is reduced to-30 ℃, the alkaline water solution is adjusted to be 2-30wt% of the alkaline concentration, and a stabilizer is added to obtain chitosan spinning stock solution;
A3, when the mixture of chitosan with the deacetylation degree higher than 50% and the aqueous alkali solution is obtained in the step (1), removing the aqueous alkali solution in the mixture in the step (1), and dissolving the obtained solid component by using a weak base aqueous solution to obtain a chitosan spinning stock solution, wherein the weak base is a bicarbonate aqueous solution;
A4, when the mixture of chitosan with the deacetylation degree higher than 50% and the aqueous alkali solution is obtained in the step (1), removing the aqueous alkali solution in the mixture in the step (1), dissolving the obtained solid component by using a dilute acid aqueous solution, adding a proper amount of alkali for neutralization, and stirring to obtain chitosan spinning stock solution;
(3) Spinning the chitin spinning solution or the chitosan spinning solution obtained in the step (2), and then regenerating in a coagulating bath to obtain chitin or chitosan fibers;
(4) Performing post-drawing, combining and twisting treatment on the chitin or chitosan fiber obtained in the step (3) to obtain yarn;
(5) And (3) adopting hot and humid steam to carry out shaping treatment on the single fiber or yarn, putting the single fiber or yarn into a standard atmosphere for balancing and sterilizing to obtain a monofilament suture or a suture with a certain specification.
2. The method for preparing the chitin/chitosan-based surgical suture according to claim 1, wherein: in the step (1), the aqueous alkali solution is KOH aqueous solution or NaOH aqueous solution or mixed solution of KOH and NaOH.
3. The method for preparing the chitin/chitosan-based surgical suture according to claim 1, wherein: in the step (2), the concentration of the chitin or chitosan in the chitin spinning solution or the chitosan spinning solution is 1-15 wt%.
4. The method for preparing the chitin/chitosan-based surgical suture according to claim 1, wherein: in the step (2), the stabilizer is one or more of urea, thiourea and polyvinyl alcohol, and the concentration of the stabilizer in the chitin spinning solution or the chitosan spinning solution is 0-20wt%.
5. The method for preparing the chitin/chitosan-based surgical suture according to claim 1, wherein: the method for adjusting the alkali concentration in the mixture in the step (2) is any one of the following methods: a. adding water to the mixture obtained in the step (1) for dilution so as to reduce the concentration of alkali; b. filtering, washing and drying the mixture in the step (1), and then adding the mixture into an aqueous solution of alkali with target concentration to reduce the concentration of the alkali; c. adjusting the alkali concentration of the mixture in the step (1) to 20-60 wt%, reducing the temperature of the mixed solution to not more than 30 ℃ and standing for a period of time, and adding ice cubes or ice water to dilute the alkali concentration to 5-30 wt%.
6. The method for preparing the chitin/chitosan-based surgical suture according to claim 1, wherein: the weak alkali aqueous solution in the step (2) is a single bicarbonate aqueous solution or a mixture of multiple bicarbonate aqueous solutions, and the concentration of the bicarbonate aqueous solution is not 2-10wt%; the dilute acid is one or a mixture of inorganic acid and organic acid, the concentration of the dilute acid aqueous solution is 1-4wt%, the neutralized alkali is at least one of alkaline hydroxide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal bicarbonate, alkaline earth metal bicarbonate, ammonia water, ammonium carbonate and ammonium bicarbonate, and the concentration of the neutralized alkali is 2-30wt%.
7. The method for preparing the chitin/chitosan-based surgical suture according to claim 1, wherein: in the step (3), the spinning method comprises wet spinning and dry-jet wet spinning, and the coagulating bath for spinning is a single coagulating bath or a multi-stage coagulating bath; the coagulating bath is one or a mixture solution of a plurality of water, saline solution and water-soluble low-viscosity organic liquid; the salt is a salt containing monovalent, divalent, trivalent cations or anions; the low viscosity organic liquid of the aqueous soluble is at least one of an alcohol, a ketone, an ester, an amide, and an organosulfide.
8. The method for preparing chitin/chitosan-based surgical suture as claimed in claim 7, wherein: the coagulating bath temperature for spinning is-10-80 deg.c, the water washing temperature is 20-80 deg.c and the drawing ratio is 1-2.5.
9. The method for efficiently preparing a chitin/chitosan-based surgical suture according to claim 1, wherein: the diameter of the spinning nozzle used for spinning is 0.08-0.8 mm.
10. A preparation method of a functional chitin/chitosan-based surgical suture is characterized in that: preparing a chitin/chitosan-based surgical suture by the method of any one of claims 1-9, introducing and crosslinking agent or functional additive during the preparation process to obtain a functional chitin/chitosan-based surgical suture; the functional additive is added through a spinning dope or coagulation bath.
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