CN108729225B - Preparation method of carboxymethyl chitosan sizing chitosan fiber - Google Patents

Preparation method of carboxymethyl chitosan sizing chitosan fiber Download PDF

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Publication number
CN108729225B
CN108729225B CN201810387628.XA CN201810387628A CN108729225B CN 108729225 B CN108729225 B CN 108729225B CN 201810387628 A CN201810387628 A CN 201810387628A CN 108729225 B CN108729225 B CN 108729225B
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chitosan
sizing
fiber
chitosan fiber
carboxymethyl chitosan
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CN108729225A (en
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孙宾
胡广敏
朱美芳
黄伦强
纪晓寰
杜衍涛
楼佳铭
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HISMER BIO-TECHNOLOGY Co Ltd
Donghua University
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HISMER BIO-TECHNOLOGY Co Ltd
Donghua University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • 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
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06—At least partially resorbable materials
    • A61L17/10—At least partially resorbable materials containing macromolecular materials
    • 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
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/14—Post-treatment to improve physical properties
    • 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
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/14—Post-treatment to improve physical properties
    • A61L17/145—Coating
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic System
    • D—TEXTILES; PAPER
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres

Abstract

The invention relates to a preparation method of carboxymethyl chitosan sizing chitosan fiber, firstly, the chitosan fiber formed by wet spinning is axially stretched in a swelling agent, and is dried after being cleaned, so as to obtain enhanced chitosan fiber; then dissolving carboxymethyl chitosan in water, preparing a crosslinked carboxymethyl chitosan sizing agent through vacuum defoaming treatment, immersing the reinforced chitosan fiber into the crosslinked carboxymethyl chitosan sizing agent for uniform sizing, drying, immersing the sized reinforced chitosan fiber into a crosslinking agent solution for crosslinking, and drying to obtain the carboxymethyl chitosan sizing chitosan fiber. The method has the advantages of simple operation, low production cost, economy, environmental protection, low energy consumption and the like, and compared with the chitosan fiber, the breaking strength of the prepared carboxymethyl chitosan sizing chitosan fiber is improved by 88.4-114.5%, the orientation degree is improved by 35.2-43.4%, and the knotting strength is improved by 81.9-109.4%, so that the method has a great application prospect.

Description

Preparation method of carboxymethyl chitosan sizing chitosan fiber
Technical Field
The invention belongs to the field of fiber reinforcement, and relates to a preparation method of carboxymethyl chitosan sizing chitosan fiber.
Background
The chitosan fiber belongs to a natural material, has the advantages of no toxicity, hemostasis, inflammation diminishing and the like, has good compatibility with biological cells, has small immunogenicity, and does not generate rejection reaction with body fluid and cells; the biodegradable chitosan can be biodegraded, and the degradation product in organisms is glucosamine; glucosamine is harmless to human bodies and does not accumulate in the bodies, so chitosan has wide application prospect in the field of biological medicines. The chitosan and its derivatives can be used as tissue scaffold, drug carrier, etc., and have effects of promoting wound healing, preventing tissue adhesion, resisting blood coagulation, reducing blood lipid, reducing cholesterol, resisting ulcer, resisting tumor, etc., and can also be blended with other fibers to make clothing material. However, the main reason for restricting the development of chitosan fiber under the influence of raw materials is that the mechanical strength of chitosan fiber is not high, and the breaking strength of chitosan fiber obtained by conventional spinning is only 1.07cN/dtex, which is far from the requirement of practical application. Therefore, the chitosan fiber is enhanced to improve the mechanical property of the chitosan fiber. Common methods for enhancing chitosan fibers include: the cross-linking enhancement, the composite enhancement and the enhancement in the spinning forming process are adopted, the chitosan fiber adopts cross-linking enhancement, namely, bifunctional substances are adopted to cross-link the chitosan fiber, the acting force among macromolecular chains is increased, the cross-linking reaction in the cross-linking enhancement generally only occurs on the surface of the fiber, and the enhancement degree is limited; the composite reinforcement is that other functional materials are mixed with chitosan for use, so that the advantages of all the materials can be comprehensively utilized, but the biocompatibility of the chitosan can be influenced along with the introduction of other substances; the drafting fiber in the spinning forming mainly adopts the hot drawing, the intermolecular action is weakened by the temperature rise, but the hot drawing needs to continuously provide heat, and the energy consumption is larger.
The fiber is generally subjected to sizing treatment before application, wherein the sizing mainly comprises coating of surface sizing agent on the fiber/yarn and filling of yarn bundles, and the thickness, uniformity and permeability of the sizing agent on the surface of the warp have great influence on the performance of the warp. The traditional sizing mode is mainly a pulp soaking mode, and in recent years, the main progress is in aspects of high-pressure sizing, prewetting sizing, cold sizing, pulp dragging type sizing, online detection and the like. The high-pressure sizing can compact the yarn structure, increase the wear resistance, reduce the hairiness and improve the efficiency of the weaving machine; the pre-wetting sizing can improve the pulp suction condition, but the concentration of the pulp in the pulp tank can generate large fluctuation; in the common sizing, sizing agent molecules are mainly connected through intermolecular force, and the mechanical property of the fiber is enhanced to a limited extent. The mechanical property of the fiber/yarn can be obviously improved by adopting the cross-linking sizing agent for sizing. At present, the crosslinking process of crosslinking modification is performed before sizing, and the concentration of sizing agent is increased in the crosslinking process, so that subsequent sizing is not facilitated.
The Chinese patent publication discloses a Chinese patent with the application number: CN201510182592.8, entitled as a patent application of a medium-temperature textile sizing method, which mainly comprises the following steps of preparing and sizing agent, adding required clear water into a size mixing barrel, starting stirring, adding an obtained dried sizing agent into the size mixing barrel, adding common unmodified starch into the size mixing barrel, stirring, adding the dried sizing agent obtained in the first step again, continuing stirring, then starting introducing steam for heating, stopping introducing steam after heating, keeping the temperature for stirring for 30 minutes, conveying the mixture into a size tank by a pump, starting a sizing machine, and starting sizing. In the method, the cross-linking agent is added into the sizing agent, but the viscosity of the sizing agent is increased before the cross-linking reaction occurs, so that the sizing is not facilitated.
Therefore, it is a technical problem to be solved at present to study a preparation method of carboxymethyl chitosan sizing chitosan fiber which is simple in operation, low in production cost, low in energy consumption and capable of remarkably improving the mechanical property and strength of chitosan fiber after sizing by a cross-linking reaction of a sizing agent.
Disclosure of Invention
Aiming at the defects of high production cost and poor mechanical property of chitosan fiber, increased viscosity of slurry caused by a crosslinking reaction before sizing and the like in the prior art, the invention provides a method for obviously improving the mechanical strength of the chitosan fiber, adopts a method for stretching and enhancing the chitosan fiber in a swelling state, weakens intermolecular acting force by adjusting the concentration of a swelling agent, improves the orientation degree and the crystallinity degree of the chitosan fiber, improves the mechanical strength of the chitosan fiber and effectively reduces energy consumption; the in-situ crosslinking technology is adopted to ensure that the crosslinking reaction is carried out after sizing, so that the problem that the sizing is not facilitated due to the increase of the concentration of the crosslinking sizing agent is solved, a compact space network structure is formed after the crosslinking reaction of the starch sizing agent, the acting force among molecular chains is increased, and the strength of the sizing chitosan fiber bundle is obviously enhanced.
In order to achieve the purpose, the invention adopts the technical scheme that:
a carboxymethyl chitosan sizing chitosan fiber preparation method, at first, make chitosan fiber finished product axially stretch in swelling agent, dry after washing, get the reinforced chitosan fiber; then dissolving carboxymethyl chitosan in water, preparing a crosslinked carboxymethyl chitosan sizing agent through vacuum defoaming treatment, immersing the reinforced chitosan fiber into the crosslinked carboxymethyl chitosan sizing agent for uniform sizing, drying, immersing the sized reinforced chitosan fiber into a crosslinking agent solution for crosslinking, and drying to obtain carboxymethyl chitosan sizing chitosan fiber;
the chitosan fiber finished product is formed by wet spinning, the chitosan fiber formed by wet spinning is a multifilament fiber, the multifilament fiber is stretched, and the tension of the stretching is better controlled, but the protection scope of the invention is not limited to the multifilament fiber, and the monofilament fiber can also be suitable for the invention, only the tension is different from that of the invention;
compared with chitosan fiber, the breaking strength of the carboxymethyl chitosan sizing chitosan fiber is improved by 88.4-114.5, the orientation degree is improved by 35.2-43.4%, and the knotting strength is improved by 81.9-109.4%.
As a preferred technical scheme:
according to the preparation method of the carboxymethyl chitosan sizing chitosan fiber, the swelling agent is dilute acetic acid, dilute hydrochloric acid, oxalic acid or citric acid, the pH value of the swelling agent is 6.0-6.5, the swelling purpose cannot be achieved when the pH value of the swelling agent is too high, and the chitosan can be dissolved when the pH value is too low. The scope of the present invention is not limited thereto, and any solvent capable of achieving the swelling function of the fiber may be applied to the present invention; the axial stretching in the swelling agent means that the chitosan fiber finished product is completely immersed in the swelling agent, and the chitosan fiber finished product can be partially immersed in the swelling agent, namely the chitosan fiber finished product is axially stretched, so that the chitosan fiber can be reinforced, but the reinforcing effect is slightly poor.
According to the preparation method of the carboxymethyl chitosan sizing chitosan fiber, the tension of axial stretching is 80-350 cN, the stretching temperature is 25-40 ℃, the stretching multiple is 1.1-1.9 times, and the stretching time is 1-3 h; the tension is too low, the molecular chain can not move under the action of the tension, the tension is too high, the fiber can be pulled apart, the swelling process of the chitosan needs a certain time, the time is short, and the purpose of swelling can not be achieved; the cleaning is to put the stretched fiber into deionized water for soaking for 0.5-1 h, the cleaning aims at removing redundant hydrogen ions, the time is too short, the hydrogen ions cannot be completely removed, and the production efficiency is affected due to too long time.
According to the preparation method of the carboxymethyl chitosan sizing chitosan fiber, the drying adopts a drying mode, the drying temperature is 60-80 ℃, and the time is 3-4 hours; the chitosan fiber finished product is dried in advance at the temperature of 60-80 ℃ for 1-3 h.
According to the preparation method of the carboxymethyl chitosan sizing chitosan fiber, the mass ratio of the carboxymethyl chitosan to water is 2-7: 100-150. The proportion is too small, the viscosity of the slurry is low, and the sizing rate is low; too large a proportion, high viscosity of the slurry, poor permeability of the slurry, and no use of sizing.
According to the preparation method of the carboxymethyl chitosan sizing chitosan fiber, the carboxymethyl chitosan is dissolved in water by stirring at the speed of 200-250 rpm. The stirring speed is low, and the dissolving time is long; too high a stirring rate may cut the macromolecular chains of chitosan, resulting in a decrease in molecular weight.
According to the preparation method of the carboxymethyl chitosan sizing chitosan fiber, the drying temperature is 45-60 ℃. Too high a drying temperature of chitosan can cause its decomposition.
In the above method for preparing carboxymethyl chitosan sizing chitosan fiber, the cross-linking agent solution is Ca2+The concentration of the aqueous solution of (1) is 3 to 9 wt%. The concentration was too low, the degree of crosslinking was insufficient, while the concentration reached 9 wt%, and the degree of crosslinking reached saturation. Ca2+The aqueous solution can be calcium chloride aqueous solution, calcium dihydrogen phosphate aqueous solution, calcium nitrate aqueous solution, calcium bicarbonate aqueous solution, calcium hydrogen sulfate aqueous solution, calcium hydrogen sulfite aqueous solution, calcium hypochlorite aqueous solution, calcium bromide aqueous solution, calcium iodide aqueous solution, calcium chlorate aqueous solution, calcium perchlorate aqueous solution, calcium permanganate aqueous solution, and other Ca-containing aqueous solution2+Aqueous solutions of (a) may also be suitable for use in the present invention.
According to the preparation method of the carboxymethyl chitosan sizing chitosan fiber, the crosslinking time is 5-10 min. The crosslinking time is short, and the crosslinking is incomplete; crosslinking for 10min, the degree of crosslinking reaches saturation and no longer increases with increasing crosslinking time.
According to the preparation method of the carboxymethyl chitosan sizing chitosan fiber, the carboxymethyl chitosan sizing chitosan fiber is coated with the coloring agent, then is dried, is immersed in the medical alcohol for 30-60 min, is sterilized and disinfected, and finally is dried and packaged in vacuum to obtain the medical suture.
The invention mechanism is as follows:
the molecular chain of the chitosan fiber contains a large amount of amino, and the amino is combined with ionized hydrogen ions in acid to form NH3 +The chitosan is converted into the cationic polymer electrolyte, the hydrogen bond structure is destroyed, the molecular chain is disentangled to a certain degree, and a swelling body is formed. When the amount of the cationic polymer electrolyte in the solution reaches a certain amount, the swelling degree of the chitosan macromolecules is increased until the chitosan macromolecules are completely dissolved. The chitosan fiber in the swelling state has weak intermolecular force, and the fiber is in a stretching state due to the existence of tension, so that molecular chains are formedThe orientation degree and the crystallinity degree are increased along with the increase of the external tension, the crystallization tends to be complete, and the strength and the modulus of the fiber are obviously improved.
The swelling and stretching chitosan fiber is subjected to sizing crosslinking, and the sizing agent is crosslinked, so that the bonding strength of the sizing agent and the fiber/yarn can be obviously improved.
The method adopts the in-situ crosslinking technology that chitosan fiber sizing is not used, firstly performs sizing and drying on the chitosan fiber, and then immerses the sized chitosan fiber into the crosslinking agent for crosslinking, thereby ensuring that the crosslinking reaction occurs after sizing, and avoiding the problem of viscosity increase of the sizing agent. Compared with the existing sizing mode after crosslinking, the sizing and crosslinking treatment technology avoids the problem of viscosity increase of the sizing agent on one hand, and on the other hand, the crosslinking agent, the sizing agent and the fibers are combined more tightly after sizing and crosslinking, so that the crosslinking degree and the sizing rate of the obtained product are better, and the product performance is better.
Has the advantages that:
(1) the invention utilizes the swelling effect of the dilute acid on the chitosan fiber, ensures that the fiber is in a stretching state due to the existence of tension, increases the orientation degree and the crystallinity of a fiber molecular chain, enlarges crystal grains, leads the crystallization to be complete, and is beneficial to improving the strength and the modulus of the fiber;
(2) the invention is crosslinked after sizing, avoids the problems that the concentration of crosslinked sizing agent is increased and sizing is not facilitated, and has wide application prospect;
(3) the method for swelling treatment and crosslinking sizing treatment of chitosan fiber has the advantages of simple process, convenient operation, low cost, low energy consumption and the like, and has great industrial application value;
(4) the carboxymethyl chitosan sizing chitosan fiber prepared by the invention has wide application and can be prepared into medical sutures.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of carboxymethyl chitosan sizing chitosan fiber comprises the following steps:
(1) pre-drying chitosan fibers formed by wet spinning at 75 ℃ for 1.5h, completely immersing the chitosan fibers in a water tank filled with dilute acetic acid with the pH value of 6.0, axially stretching the chitosan fibers for 1h under the conditions of the tension of 210cN, the stretching temperature of 40 ℃ and the stretching multiple of 1.5, finally soaking the stretched fibers in deionized water for 0.8h, and drying the fibers at 70 ℃ for 3h to obtain the reinforced chitosan fibers;
(2) stirring and dissolving carboxymethyl chitosan in water at the speed of 200rpm, and performing vacuum defoaming treatment to prepare a crosslinked carboxymethyl chitosan sizing agent, wherein the mass ratio of the carboxymethyl chitosan to the water is 3: 120;
(3) soaking the reinforced chitosan fiber prepared in the step (1) into a crosslinked carboxymethyl chitosan sizing agent for uniform sizing, drying at the temperature of 55 ℃, soaking the sized chitosan fiber into a calcium chloride aqueous solution with the concentration of 3 wt% for crosslinking for 8min, and drying at the temperature of 55 ℃ to prepare the carboxymethyl chitosan sizing chitosan fiber, wherein the breaking strength of the carboxymethyl chitosan sizing chitosan fiber is increased by 88.4% compared with that of the chitosan fiber, the orientation degree is increased by 35.2%, and the knotting strength is increased by 88.2%.
And (3) spraying a coloring agent on the carboxymethyl chitosan sizing chitosan fiber prepared by the method, drying, immersing in medical alcohol for 30min, and finally, drying and packaging in vacuum to obtain the medical suture.
Example 2
A preparation method of carboxymethyl chitosan sizing chitosan fiber comprises the following steps:
(1) pre-drying chitosan fibers formed by wet spinning at 60 ℃ for 3 hours, completely immersing the chitosan fibers in a water tank filled with dilute acetic acid with the pH value of 6.3, axially stretching the chitosan fibers for 2 hours under the conditions of the tension of 80cN, the stretching temperature of 35 ℃ and the stretching multiple of 1.1, finally soaking the stretched fibers in deionized water for 0.5 hour, and drying the fibers at 65 ℃ for 3.5 hours to obtain the reinforced chitosan fibers;
(2) stirring and dissolving carboxymethyl chitosan in water at the speed of 220rpm, and performing vacuum defoaming treatment to prepare a crosslinked carboxymethyl chitosan sizing agent, wherein the mass ratio of the carboxymethyl chitosan to the water is 5: 100;
(3) soaking the reinforced chitosan fiber prepared in the step (1) into a cross-linked carboxymethyl chitosan sizing agent for uniform sizing, drying at the temperature of 45 ℃, finally soaking the sized chitosan fiber into a calcium dihydrogen phosphate aqueous solution with the concentration of 9 wt% for cross-linking for 6min, and drying at the temperature of 40 ℃ to prepare the carboxymethyl chitosan sizing chitosan fiber, wherein the breaking strength of the carboxymethyl chitosan sizing chitosan fiber is improved by 114.5% compared with that of the chitosan fiber, the orientation degree is improved by 37.5%, and the knotting strength is improved by 96.4%.
And (3) spraying a coloring agent on the carboxymethyl chitosan sizing chitosan fiber prepared by the method, drying, immersing in medical alcohol for 40min, and finally, drying and packaging in vacuum to obtain the medical suture.
Example 3
A preparation method of carboxymethyl chitosan sizing chitosan fiber comprises the following steps:
(1) pre-drying chitosan fibers formed by wet spinning at 65 ℃ for 2 hours, completely immersing the chitosan fibers in a water tank filled with dilute acetic acid with the pH value of 6.1, axially stretching the chitosan fibers for 1.5 hours under the conditions of the tension of 300cN, the stretching temperature of 25 ℃ and the stretching multiple of 1.8, finally soaking the stretched fibers in deionized water for 0.6 hour, and drying the fibers at 60 ℃ for 4 hours to obtain the reinforced chitosan fibers;
(2) stirring and dissolving carboxymethyl chitosan in water at the speed of 250rpm, and performing vacuum defoaming treatment to prepare a crosslinked carboxymethyl chitosan sizing agent, wherein the mass ratio of the carboxymethyl chitosan to the water is 4: 130;
(3) and (2) soaking the reinforced chitosan fiber prepared in the step (1) into a crosslinked carboxymethyl chitosan sizing agent for uniform sizing, drying at 50 ℃, finally soaking the sized chitosan fiber into a calcium nitrate aqueous solution with the concentration of 6 wt% for crosslinking for 7min, and drying at 50 ℃ to prepare the carboxymethyl chitosan sized chitosan fiber, wherein the breaking strength of the carboxymethyl chitosan sized chitosan fiber is improved by 111.3% compared with that of the chitosan fiber, the orientation degree is improved by 40.8%, and the knotting strength is improved by 83.9%.
And (3) spraying a coloring agent on the carboxymethyl chitosan sizing chitosan fiber prepared by the method, drying, immersing in medical alcohol for 50min, and finally, drying and packaging in vacuum to obtain the medical suture.
Example 4
A preparation method of carboxymethyl chitosan sizing chitosan fiber comprises the following steps:
(1) pre-drying chitosan fibers formed by wet spinning at 75 ℃ for 1 hour, completely immersing the chitosan fibers in a water tank filled with dilute hydrochloric acid with the pH value of 6.5, axially stretching the chitosan fibers for 3 hours under the conditions of the tension of 180cN, the stretching temperature of 30 ℃ and the stretching multiple of 1.4, finally soaking the stretched fibers in deionized water for 1 hour, and drying the fibers at 75 ℃ for 4 hours to obtain the reinforced chitosan fibers;
(2) stirring and dissolving carboxymethyl chitosan in water at the speed of 210rpm, and performing vacuum defoaming treatment to prepare a crosslinked carboxymethyl chitosan sizing agent, wherein the mass ratio of the carboxymethyl chitosan to the water is 2: 150;
(3) and (2) soaking the reinforced chitosan fiber prepared in the step (1) into a crosslinked carboxymethyl chitosan sizing agent for uniform sizing, drying at the temperature of 45 ℃, finally soaking the sized chitosan fiber into a 7 wt% calcium bicarbonate aqueous solution for crosslinking for 10min, and drying at the temperature of 45 ℃ to prepare the carboxymethyl chitosan sized chitosan fiber, wherein the breaking strength of the carboxymethyl chitosan sized chitosan fiber is improved by 106.8% compared with that of the chitosan fiber, the orientation degree is improved by 43.4%, and the knotting strength is improved by 100.5%.
And (3) spraying a coloring agent on the carboxymethyl chitosan sizing chitosan fiber prepared by the method, drying, immersing in medical alcohol for 45min, and finally, drying and packaging in vacuum to obtain the medical suture.
Example 5
A preparation method of carboxymethyl chitosan sizing chitosan fiber comprises the following steps:
(1) pre-drying chitosan fibers formed by wet spinning at 70 ℃ for 2.5h, completely immersing the chitosan fibers in a water tank filled with dilute hydrochloric acid with the pH value of 6.2, axially stretching the chitosan fibers for 2.5h under the conditions of the tension of 350cN, the stretching temperature of 40 ℃ and the stretching multiple of 1.9, finally soaking the stretched fibers in deionized water for 0.5h, and drying the fibers at 80 ℃ for 3h to obtain the reinforced chitosan fibers;
(2) stirring and dissolving carboxymethyl chitosan in water at the speed of 200rpm, and performing vacuum defoaming treatment to prepare a crosslinked carboxymethyl chitosan sizing agent, wherein the mass ratio of the carboxymethyl chitosan to the water is 7: 110;
(3) soaking the reinforced chitosan fiber prepared in the step (1) into a crosslinked carboxymethyl chitosan sizing agent for uniform sizing, drying at the temperature of 60 ℃, finally soaking the sized chitosan fiber into a calcium bisulfate aqueous solution with the concentration of 5 wt% for crosslinking for 9min, and drying at the temperature of 60 ℃ to prepare the carboxymethyl chitosan sizing chitosan fiber, wherein the breaking strength of the carboxymethyl chitosan sizing chitosan fiber is improved by 99.6% compared with that of the chitosan fiber, the orientation degree is improved by 42.8%, and the knotting strength is improved by 81.9%.
And (3) spraying a coloring agent on the carboxymethyl chitosan sizing chitosan fiber prepared by the method, drying, immersing in medical alcohol for 60min, and finally, drying and packaging in vacuum to obtain the medical suture.
Example 6
A preparation method of carboxymethyl chitosan sizing chitosan fiber comprises the following steps:
(1) pre-drying chitosan fibers formed by wet spinning at 80 ℃ for 3 hours, completely immersing the chitosan fibers in a water tank filled with dilute hydrochloric acid with the pH value of 6.0, axially stretching the chitosan fibers for 2 hours under the conditions of tension of 120cN, stretching temperature of 25 ℃ and stretching multiple of 1.2, finally soaking the stretched fibers in deionized water for 0.9 hour, and drying the fibers at 60 ℃ for 4 hours to obtain the reinforced chitosan fibers;
(2) stirring and dissolving carboxymethyl chitosan in water at the speed of 240rpm, and performing vacuum defoaming treatment to prepare a crosslinked carboxymethyl chitosan sizing agent, wherein the mass ratio of the carboxymethyl chitosan to the water is 3: 140;
(3) soaking the reinforced chitosan fiber prepared in the step (1) into a crosslinked carboxymethyl chitosan sizing agent for uniform sizing, drying at the temperature of 55 ℃, finally soaking the sized chitosan fiber into a 9 wt% calcium chlorate aqueous solution for crosslinking for 5min, and drying at the temperature of 55 ℃ to prepare the carboxymethyl chitosan sizing chitosan fiber, wherein the breaking strength of the carboxymethyl chitosan sizing chitosan fiber is improved by 109.7% compared with that of the chitosan fiber, the orientation degree is improved by 39.2%, and the knot strength is improved by 94.3%.
And (3) spraying a coloring agent on the carboxymethyl chitosan sizing chitosan fiber prepared by the method, drying, immersing in medical alcohol for 50min, and finally, drying and packaging in vacuum to obtain the medical suture.
Example 7
A preparation method of carboxymethyl chitosan sizing chitosan fiber comprises the following steps:
(1) pre-drying chitosan fibers formed by wet spinning at 65 ℃ for 1.5h, completely immersing the chitosan fibers in a water tank filled with oxalic acid with the pH value of 6.5, axially stretching the chitosan fibers for 2h under the conditions of the tension of 300cN, the stretching temperature of 25 ℃ and the stretching multiple of 1.8, finally soaking the stretched fibers in deionized water for 0.6h, and drying the fibers at 80 ℃ for 4h to obtain the reinforced chitosan fibers;
(2) stirring and dissolving carboxymethyl chitosan in water at the speed of 250rpm, and performing vacuum defoaming treatment to prepare a crosslinked carboxymethyl chitosan sizing agent, wherein the mass ratio of the carboxymethyl chitosan to the water is 5: 130;
(3) and (2) soaking the reinforced chitosan fiber prepared in the step (1) into a cross-linked carboxymethyl chitosan sizing agent for uniform sizing, drying at the temperature of 45 ℃, finally soaking the sized chitosan fiber into a calcium bromide aqueous solution with the concentration of 4 wt% for cross-linking for 6min, and drying at the temperature of 50 ℃ to prepare the carboxymethyl chitosan sizing chitosan fiber, wherein the breaking strength of the carboxymethyl chitosan sizing chitosan fiber is improved by 97.5% compared with that of the chitosan fiber, the orientation degree is improved by 40.5%, and the knotting strength is improved by 102.8%.
And (3) spraying a coloring agent on the carboxymethyl chitosan sizing chitosan fiber prepared by the method, drying, immersing in medical alcohol for 40min, and finally, drying and packaging in vacuum to obtain the medical suture.
Example 8
A preparation method of carboxymethyl chitosan sizing chitosan fiber comprises the following steps:
(1) pre-drying chitosan fibers formed by wet spinning at 70 ℃ for 3 hours, completely immersing the chitosan fibers in a water tank filled with citric acid with the pH value of 6.4, axially stretching the chitosan fibers for 3 hours under the conditions of the tension of 290cN, the stretching temperature of 40 ℃ and the stretching multiple of 1.7, finally soaking the stretched fibers in deionized water for 0.5 hour, and drying the fibers at 60 ℃ for 3 hours to obtain the reinforced chitosan fibers;
(2) stirring and dissolving carboxymethyl chitosan in water at the speed of 230rpm, and performing vacuum defoaming treatment to prepare a crosslinked carboxymethyl chitosan sizing agent, wherein the mass ratio of the carboxymethyl chitosan to the water is 6: 100;
(3) soaking the reinforced chitosan fiber prepared in the step (1) into a cross-linked carboxymethyl chitosan sizing agent for uniform sizing, drying at the temperature of 50 ℃, finally soaking the sized chitosan fiber into a calcium permanganate aqueous solution with the concentration of 3 wt% for crosslinking for 8min, and drying at the temperature of 45 ℃ to prepare the carboxymethyl chitosan sizing chitosan fiber, wherein the breaking strength of the carboxymethyl chitosan sizing chitosan fiber is improved by 90.3% compared with that of the chitosan fiber, the orientation degree is improved by 41.4%, and the knotting strength is improved by 109.4%.
And (3) spraying a coloring agent on the carboxymethyl chitosan sizing chitosan fiber prepared by the method, drying, immersing in medical alcohol for 30min, and finally, drying and packaging in vacuum to obtain the medical suture.

Claims (10)

1. A preparation method of carboxymethyl chitosan sizing chitosan fiber is characterized in that: firstly, axially stretching a chitosan fiber finished product in a swelling agent, cleaning and drying to obtain reinforced chitosan fiber; then dissolving carboxymethyl chitosan in water, preparing carboxymethyl chitosan sizing agent through vacuum defoaming treatment, immersing the reinforced chitosan fiber into the carboxymethyl chitosan sizing agent for uniform sizing, drying, immersing the sized reinforced chitosan fiber into a cross-linking agent solution for cross-linking, and drying to obtain carboxymethyl chitosan sizing chitosan fiber;
the swelling agent is dilute acetic acid, dilute hydrochloric acid, oxalic acid or citric acid;
the chitosan fiber finished product is formed by wet spinning;
compared with the finished product of the chitosan fiber, the fracture strength of the carboxymethyl chitosan sizing chitosan fiber is improved by 88.4-114.5%, the orientation degree is improved by 35.2-43.4%, and the knotting strength is improved by 81.9-109.4%.
2. The method for preparing carboxymethyl chitosan sizing chitosan fiber according to claim 1, wherein the pH of the swelling agent is 6.0-6.5; the axial stretching in the swelling agent is carried out by completely immersing the chitosan fiber finished product in the swelling agent.
3. The preparation method of carboxymethyl chitosan sizing chitosan fiber according to claim 1, wherein the tension of axial stretching is 80-350 cN, the stretching temperature is 25-40 ℃, the stretching ratio is 1.1-1.9 times, and the stretching time is 1-3 h; and the cleaning step is to soak the stretched fiber in deionized water for 0.5-1 h.
4. The preparation method of carboxymethyl chitosan sizing chitosan fiber according to claim 1, wherein the drying is performed in a drying manner, the drying temperature is 60-80 ℃, and the drying time is 3-4 h; the chitosan fiber finished product is dried in advance at the temperature of 60-80 ℃ for 1-3 h.
5. The preparation method of carboxymethyl chitosan sizing chitosan fiber according to claim 1, wherein the mass ratio of carboxymethyl chitosan to water is 2-7: 100-150.
6. The method for preparing carboxymethyl chitosan sizing chitosan fiber according to claim 1, wherein the carboxymethyl chitosan is dissolved in water by stirring at a speed of 200-250 rpm.
7. The method for preparing carboxymethyl chitosan sizing chitosan fiber according to claim 1, wherein the drying temperature is 45-60 ℃.
8. The method for preparing carboxymethyl chitosan sizing chitosan fiber according to claim 1, wherein the cross-linking agent solution is Ca2+The concentration of the aqueous solution of (1) is 3 to 9 wt%.
9. The method for preparing carboxymethyl chitosan sizing chitosan fiber according to claim 1, wherein the crosslinking time is 5-10 min.
10. The preparation method of carboxymethyl chitosan sizing chitosan fiber according to claim 1, wherein the carboxymethyl chitosan sizing chitosan fiber is dried after being coated with a coloring agent, then is immersed in medical alcohol for 30-60 min, and finally is vacuum-dried and packaged to obtain the medical suture.
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