CN106478825B - Method for preparing oxidized cellulose for hemostasis in ramie oxidation degumming process - Google Patents
Method for preparing oxidized cellulose for hemostasis in ramie oxidation degumming process Download PDFInfo
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Abstract
The invention provides a method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie, which takes ramie as raw material, firstly, the raw ramie is crushed into short fiber, and the short fiber is soaked to be fully wetted and swelled; then mixing the pretreated raw hemp short fiber with the degumming solution, heating and preserving heat, fully removing colloid in the raw hemp by using the oxidizability of a specific oxidant, and simultaneously oxidizing cellulose with active hydroxyl into oxidized cellulose containing a large amount of carboxyl; soaking the oxidized fiber in an organic solvent aqueous solution to remove unreacted oxidant; and finally, separating the oxidized cellulose from water, and drying to obtain the powdered oxidized cellulose for hemostasis. The method provided by the invention has simple flow, combines the original two processes into one process, shortens the total reaction time, saves the medicines and the cost, and greatly improves the efficiency. The obtained product has the advantages of high hemostasis speed, high hemostasis efficiency and stable effect, and can be widely applied to rapid hemostasis in conditions of war wounds, wounds and the like.
Description
Technical Field
The invention relates to a method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie, belonging to the technical field of natural fiber preparation and oxidized cellulose for hemostasis application in the textile field.
Background
In recent years, medical absorbable hemostatic materials attract high attention from various medical and industrial fields, and along with the improvement of the performance requirements of the hemostatic materials, the development of the medical absorbable hemostatic materials which have better hemostatic effect, are green, environment-friendly, degradable, non-toxic, free of side effects, non-irritant and good in biocompatibility is imperative. At present, the medical hemostatic materials mainly comprise fibrin glue, gelatin sponge, oxidized cellulose, microfibril collagen, chitosan, calcium alginate fiber and the like. The method is characterized in that the excellent biomass material is searched from the nature for processing improvement, and the novel absorbable hemostatic material with simple preparation method, low cost and good hemostatic effect is an ideal choice.
Cellulose-based hemostatic materials extracted from cotton, hemp, and various natural cellulosic materials are widely favored. Oxidized Cellulose (Oxidized Cellulose, also known as 6-carboxyl group)Cellulose) is a derivative of cellulose, has the characteristics of porosity and large specific surface area, has good biocompatibility and biodegradability, is nontoxic, and can be applied to the medical field as a hemostatic material. After the medical gauze made of oxidized cellulose is implanted into the body, the carboxyl group of the medical gauze is mixed with Ca in the blood plasma2+The cross-linking occurs, which leads to the reaction of the oxidized cellulose and the hemoglobin to form an artificial blood clot, thereby playing the role of hemostasis. At present, a commercial product of oxidized cellulose clinically used as hemostatic gauze is 'SuRGICEL' of the Proteus Corp. Natl., USA, but the existing form of the product is not favorable for being combined with other products, the production process is complex, the cost is high, the price is high, the waste of oxidizing liquid is serious in the production process, better substitute products are urgently to be developed, and the research of a better preparation process of medical hemostatic oxidized cellulose is an urgent problem.
Ramie is a natural cellulose fiber with excellent performance, and the fiber is tough, rich in luster, corrosion-resistant and not easy to mildew. The ramie contains cellulose as main component, lignin, pectin, hemicellulose and other non-cellulose components, which are collectively called as pectin. The gum wrapped around the cellulose must be removed prior to use. The oxidation degumming of ramie is a degumming method which selects a specific oxidant, cuts colloid molecules in ramie fibers, oxidizes and degrades the colloid molecules into micromolecules and simultaneously retains cellulose components. The oxidation degumming has the advantages of fast reaction time, low cost, easy operation, little pollution and low energy consumption, and is a research hotspot in the field of natural fiber preparation at present. However, some oxidants have relatively strong oxidizing property, and as the degree of oxidation increases, the primary hydroxyl group at the C6 position on the glucose ring of the cellulose macromolecular chain is easily oxidized into carboxyl group, so that oxidized cellulose (i.e. 6-carboxyl cellulose) is generated, and the oxidized cellulose has certain adsorption performance. Therefore, in the process of preparing the fiber by oxidizing and degumming the ramie, the oxidation system and the regulation and control process conditions are reasonably selected, so that multiple purposes can be achieved, the colloid component can be removed, the hydroxyl on the cellulose can be mildly oxidized into carboxyl, the oxidized cellulose with the adsorption property is generated, and the double targets of natural fiber extraction and medical hemostatic material preparation are realized, thereby achieving the purposes of reducing the flow time, saving the medicine and the cost and improving the efficiency.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie, by researching the relationship between oxidation degumming and oxidized cellulose formation and reasonably controlling the reaction process, the ramie degumming and the generation of adsorptive oxidized cellulose are carried out in the same bath at the same time, the optimal degumming effect is obtained, the cellulose adsorbent suitable for hemostasis is prepared, and the added value of the cellulose derivative is improved.
In order to solve the technical problems, the technical scheme of the invention is to provide a method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie, which is characterized by comprising the following steps: the method comprises the following 3 steps:
step 1: pretreatment of raw hemp fiber
Pulverizing ramie into short fibers, putting the short fibers into a closed container to balance moisture, and measuring the moisture regain of the short fibers; weighing the mass of the short fiber, and calculating the dry weight of the short fiber according to the moisture regain; adding deionized water into short fibers, and soaking to fully wet and swell the raw hemp cellulose;
step 2: oxidation treatment of cellulose
Preparing degumming reaction liquid from 2-10% of oxidant, 0.5-5% of cellulose protective agent, 0.5-4% of fiber expanding agent, 0.5-3% of surfactant, 0.5-3% of chelating agent and distilled water in percentage by weight; mixing the short fibers of the raw ramie with degumming reaction liquid in a reactor, adjusting the initial pH value of the degumming liquid to 3.0-14.0, putting the reactor into a constant-temperature water bath kettle, stirring the mixture in the reactor under the condition of keeping out of the sun, heating the water bath kettle to 50-100 ℃, preserving the temperature for 40-150 min, fully removing the colloid in the raw ramie by utilizing the oxidability of an oxidant, and oxidizing cellulose with hydroxyl into oxidized cellulose containing a large amount of carboxyl;
and step 3: washing and stabilizing treatment of oxidized cellulose
Soaking and washing the reacted fiber with an organic solvent to remove unreacted oxidant, and then fully washing and soaking the fiber with deionized water; centrifuging the obtained mixture for layering, transferring supernatant into another container, placing the rest concentrated cellulose suspension into a vacuum freeze-drying instrument, freeze-drying with liquid nitrogen for molding to obtain powdered oxidized cellulose adsorbent, and storing in a freezing chamber.
Preferably, in the step 1, the fineness of the crushed short fibers is 20-100 meshes, distilled water is added into the short fibers to ensure that the mass percentage concentration of the cellulose solids in the distilled water is 1-10%, and the soaking time of the distilled water is 12-48 h.
Preferably, in the step 2, the raw ramie staple fibers and the degumming reaction solution are mixed in a reactor according to the mass ratio of 1: 10; adjusting the solution used for adjusting the initial pH value of the degumming solution to be 0.1mol/L NaOH solution or 0.1mol/L HCl solution; the mixture in the reactor was stirred continuously with a magnetic stirrer at a speed of 200 rpm.
Preferably, in the step 2, the oxidizing agent is one or more of sodium bromate, sodium chlorate, sodium chlorite, a tetramethylpiperidine oxide-sodium hypochlorite-sodium bromide ternary composite oxidation system, a nitric acid-phosphoric acid-sodium nitrite oxidation system, sodium percarbonate, sodium periodate, potassium periodate, sodium hypochlorite, potassium percarbonate, sodium chlorate and sodium bromate.
Preferably, in the step 2, the cellulose protective agent is one or more of sodium polyphenyleneoxide, anthraquinone, magnesium hydroxide, polyvinyl alcohol, water glass, polyacrylamide, magnesium silicate, acetanilide, resorcinol, sodium citrate and sodium benzoate.
Preferably, in the step 2, the fiber expanding agent comprises one or two of urea, ethylenediamine, liquid ammonia, thiourea, 4-methylmorpholine-N-oxide, copper ethylenediamine and dimethyl sulfoxide.
Preferably, in the step 2, the surfactant is one or two of polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether (JFC) and peregal.
Preferably, in the step 2, the metal ion chelating agent comprises one or more of nitrilotriacetic acid, sodium ethylene diamine tetra methylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, sodium ethylene diamine dipehthalate, hydroxyethylidene diphosphonic acid and sodium salt thereof, sodium polyacrylate and sodium ethylene diamine tetra methylene phosphonic acid.
Preferably, in the step 3, the organic solvent used for the fiber after the soaking reaction is one or two of glycerol, ethylene glycol, acetone and 1, 3-propylene glycol, the concentration is 0.1mol/L, and the soaking and washing time is 0.5-2 h.
Preferably, in the step 3, the time for fully washing and soaking with deionized water is 24 hours; centrifuging and layering the prepared mixture by a centrifuge, wherein the rotating speed of the centrifuge is 6000-12000 rpm, and the centrifuging times are 3-6; the temperature of the freeze drying molding is-40 to-60 ℃, the pressure of the freeze drying molding is 10 to 60Pa, and the time of the freeze drying molding is 4 to 10 hours.
The method provided by the invention uses natural ramie fibers as raw materials to develop and develop a novel oxidized cellulose adsorbent. The method selects a specific oxidant, reasonably regulates and controls reaction process conditions, selectively oxidizes C6 primary hydroxyl on a cellulose chain into carboxyl while removing colloid components in the original hemp, changes the structure of the cellulose, endows the cellulose with new functions, enables the cellulose to become oxidized cellulose with a hemostatic function, and expands the application field of the cellulose.
The method provided by the invention overcomes the defects of the existing ramie oxidation degumming and oxidized cellulose preparation technology for hemostasis, has simple flow, combines the original two procedures into one procedure, shortens the total reaction time, saves the medicine and the cost, and greatly improves the efficiency. Meanwhile, the preparation method has the advantages of simple process, environmental friendliness, mild reaction conditions, low equipment requirements and convenience for large-scale production. The obtained product has the advantages of 2.0-2.3% of residual gum rate, 300-500% of polymerization degree, 18-22% of carboxyl content, high hemostasis speed, high hemostasis efficiency, stable effect, short in vivo absorption time, broad-spectrum sterilization and inflammation diminishing, wound healing promotion and the like, and is not influenced by the size and the position of a wound surface. Compared with the existing hemostatic medical material, the oxidized cellulose has the advantages of environmental friendliness, mild reaction conditions, low equipment requirements, good chemical stability and the like, and can be widely applied to rapid hemostasis in conditions such as war wounds, wounds and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. 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 method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie comprises the following steps:
pulverizing ramie into short fiber with fineness of 40 mesh, placing into container with sealing ring for balancing water, and measuring moisture regain of short fiber to be 9.2%. The short fiber was weighed to have a mass of 21.10g, and its dry fiber weight was 19.16g based on the moisture regain. Deionized water is added to ensure that the mass concentration of the original hemp cellulose is 6 percent, and the original hemp cellulose is soaked for 48 hours to be fully wetted. 0.4g of sodium chlorate, 0.1g of resorcinol, 0.1g of 4-methylmorpholine-N-oxide, 0.1g of polyvinyl alcohol and 0.1g of nitrilotriacetic acid are added with 199.2g of water to prepare degumming liquid; mixing the ramie raw ramie short fibers and the degumming reaction solution according to the mass ratio of 1: 10, and taking a 1000mL brown conical flask as a reactor. The pH value of the degumming solution is adjusted to 8.0 by using 0.1mol/L NaOH solution, and the mixture of the ramie raw material and the degumming solution is continuously stirred by using a magnetic stirrer at the speed of 200rpm under the condition of keeping out light. Heating the water bath to 100 deg.C, maintaining the temperature for 40min, removing colloid from ramie by oxidizing agent, and oxidizing C6 primary hydroxyl group into carboxyl group to obtain 6-carboxyl oxidized cellulose. Soaking the reacted fiber in 0.1mol/L acetone water solution for 2h, removing unreacted oxidant, and then washing and soaking the fiber in deionized water for 24 h. Finally, centrifuging and washing for 3 times by adopting a centrifuge with the rotating speed of 11000rpm, transferring the supernatant into another container, and putting the residual concentrated cellulose suspension into a vacuum freeze dryer; drying at-60 deg.C under 50Pa for 4 hr to obtain powdered oxidized cellulose adsorbent, and storing in a freezing chamber.
4 adult New Zealand rabbits (half of male and female, with a weight of 2.5-3 kg) are selected as experimental animals, pentobarbital sodium solution is injected into ear veins of the experimental rabbits to enable the rabbits to be anesthetized systemically, muscle layers on the backs of the rabbits are cut, and the exposed area is about 2cm multiplied by 2 cm. The obtained oxidized cellulose (area 1cm × 1cm) was spread on the wound surface, and the hemostatic effect was examined. The wound was closed, opened at days 6 and 9 post-test, respectively, and the absorption was observed.
The residual gum rate of the oxidized cellulose measured by boiling a 20g/L NaOH solution is 2.3 percent, the crystallinity of the oxidized cellulose measured by an X-ray diffractometer is 60.12 percent, the Degree of Polymerization (DP) of the oxidized cellulose measured by a copper ethylene diamine viscosity method is 300, and the carboxyl content of the oxidized cellulose measured by an acid-base neutralization titration method is 18.0 percent. The back muscle implantation test of the rabbits shows that the oxidized cellulose can effectively stop bleeding within 100 seconds after being pasted on the wound surface of an animal wound. The oxidized cellulose was partially degraded at day 6 and almost completely degraded at day 9.
Therefore, the method for preparing the oxidized cellulose for hemostasis in the ramie oxidation degumming process provided by the invention has the advantages of small residual gum rate of the prepared oxidized cellulose for hemostasis, moderate crystallinity and polymerization degree, high carboxyl content, high hemostasis speed, stable hemostasis performance and good absorption effect.
Example 2
A method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie comprises the following steps:
pulverizing ramie into short fiber with fineness of 20 meshes by a pulverizer, placing into a container with a sealing ring for balancing water, and measuring the moisture regain of the short fiber to be 9.2%. The short fiber weighed 21.20g and had a dry fiber weight of 19.25g based on the moisture regain. Deionized water is added to ensure that the mass concentration of the original hemp cellulose is 1 percent, and the original hemp cellulose is soaked for 24 hours to be fully wetted. Adding 197.5g of water into 1g of a tetramethylpiperidine oxide-sodium hypochlorite-sodium bromide ternary composite oxidation system, 0.5g of sodium benzoate, 0.4g of urea, 0.3g of sodium dodecyl sulfate and 0.3g of sodium polyacrylate to prepare a degumming solution; mixing the ramie raw ramie short fibers and the degumming reaction solution according to the mass ratio of 1: 10, and taking a 1000mL brown conical flask as a reactor. The pH of the degumming solution is adjusted to 3.0 with 0.1mol/L HCl solution, and the mixture of ramie material and degumming solution is continuously stirred with a magnetic stirrer at a speed of 200rpm in the dark. Heating the water bath to 85 deg.C, maintaining the temperature for 100min, removing colloid from ramie by oxidizing agent, and oxidizing C6 primary hydroxyl group into carboxyl group to obtain 6-carboxyl oxidized cellulose. Soaking the reacted fiber in 0.1mol/L glycerol water solution for 0.5h, removing unreacted oxidant, and then fully washing and soaking the fiber in deionized water for 24 h. Finally, centrifuging and washing for 4 times by adopting a centrifuge with the rotating speed of 6000rpm, transferring supernatant into another container, and putting the residual concentrated cellulose suspension into a vacuum freeze dryer; drying at-40 deg.C under 20Pa for 4 hr to obtain powdered oxidized cellulose adsorbent, and storing in a freezing chamber.
4 adult New Zealand rabbits (half of male and female, with a weight of 2.5-3 kg) are selected as experimental animals, pentobarbital sodium solution is injected into ear veins of the experimental rabbits to enable the rabbits to be anesthetized systemically, muscle layers on the backs of the rabbits are cut, and the exposed area is about 2cm multiplied by 2 cm. The obtained oxidized cellulose (area 1cm × 1cm) was spread on the wound surface, and the hemostatic effect was examined. The wound was closed, opened at days 6 and 9 post-test, respectively, and the absorption was observed.
The residual gum rate of the oxidized cellulose measured by boiling a 20g/L NaOH solution is 2.1 percent, the crystallinity of the oxidized cellulose measured by an X-ray diffractometer is 61.09 percent, the Degree of Polymerization (DP) of the oxidized cellulose measured by a copper ethylene diamine viscosity method is 500, and the carboxyl content of the oxidized cellulose measured by an acid-base neutralization titration method is 22.0 percent. The back muscle implantation test of the rabbits shows that the oxidized cellulose can effectively stop bleeding within 100 seconds after being pasted on the wound surface of an animal wound. The oxidized cellulose was partially degraded at day 6 and almost completely degraded at day 9.
Therefore, the method for preparing the oxidized cellulose for hemostasis in the ramie oxidation degumming process provided by the invention has the advantages of small residual gum rate of the prepared oxidized cellulose for hemostasis, moderate crystallinity and polymerization degree, high carboxyl content, high hemostasis speed, stable hemostasis performance and good absorption effect.
Example 3
A method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie comprises the following steps:
pulverizing ramie into short fiber with fineness of 60 mesh, placing into container with sealing ring for balancing water, and measuring moisture regain of short fiber to be 8.9%. The short fiber was weighed to have a mass of 22.02g, and its dry fiber weight was calculated to be 20.06g based on the moisture regain. Deionized water is added to ensure that the mass concentration of the original hemp cellulose is 3 percent, and the original hemp cellulose is soaked for 36 hours to be fully wetted. Preparing a degumming solution by adding 195.0g of water into 2.0g of a nitric acid-phosphoric acid-sodium nitrite oxidation system, 1.0g of water glass, 0.8g of thiourea, 0.6g of sodium dodecyl benzene sulfonate and 0.6g of diethylenetriamine pentamethylene phosphonic acid; mixing the ramie raw ramie short fibers and the degumming reaction solution according to the mass ratio of 1: 10, and taking a 1000mL brown conical flask as a reactor. The pH of the degumming solution is adjusted to 14.0 with 0.1mol/L NaOH solution, and the mixture of ramie raw material and degumming solution is continuously stirred with a magnetic stirrer at a speed of 200rpm in the dark. Heating the water bath to 50 deg.C, maintaining the temperature for 150min, removing colloid from ramie by oxidizing agent, and oxidizing C6 primary hydroxyl group into carboxyl group to obtain 6-carboxyl oxidized cellulose. Soaking the reacted fiber in 0.1mol/L glycol water solution for 1h, removing unreacted oxidant, and then fully washing and soaking the fiber in deionized water for 24 h. Finally, centrifuging and washing for 6 times by adopting a centrifuge with the rotating speed of 10000rpm, transferring the supernatant into another container, and putting the residual concentrated cellulose suspension into a vacuum freeze dryer; drying at-60 deg.C under 10Pa for 6 hr to obtain powdered oxidized cellulose adsorbent, and storing in a freezing chamber.
4 adult New Zealand rabbits (half of male and female, with a weight of 2.5-3 kg) are selected as experimental animals, pentobarbital sodium solution is injected into ear veins of the experimental rabbits to enable the rabbits to be anesthetized systemically, muscle layers on the backs of the rabbits are cut, and the exposed area is about 2cm multiplied by 2 cm. The obtained oxidized cellulose (area 1cm × 1cm) was spread on the wound surface, and the hemostatic effect was examined. The wound was closed, opened at days 6 and 9 post-test, respectively, and the absorption was observed.
The gum residue rate of the oxidized cellulose measured by boiling a 20g/L NaOH solution is 2.0%, the crystallinity of the oxidized cellulose measured by an X-ray diffractometer is 59.82%, the Degree of Polymerization (DP) of the oxidized cellulose measured by a copper ethylene diamine viscosity method is 418, and the carboxyl content of the oxidized cellulose measured by an acid-base neutralization titration method is 20.14%. The back muscle implantation test of the rabbits shows that the oxidized cellulose can effectively stop bleeding within 100 seconds after being pasted on the wound surface of an animal wound. The oxidized cellulose was partially degraded at day 6 and almost completely degraded at day 9.
Therefore, the method for preparing the oxidized cellulose for hemostasis in the ramie oxidation degumming process provided by the invention has the advantages of small residual gum rate of the prepared oxidized cellulose for hemostasis, moderate crystallinity and polymerization degree, high carboxyl content, high hemostasis speed, stable hemostasis performance and good absorption effect.
Example 4
A method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie comprises the following steps:
pulverizing ramie into short fiber with fineness of 100 mesh, placing into container with sealing ring for balancing water, and measuring moisture regain of short fiber to be 9.0%. The short fiber weighed 21.35g and had a dry fiber weight of 19.43g based on the moisture regain. Deionized water is added to ensure that the mass concentration of the original hemp cellulose is 10 percent, and the original hemp cellulose is soaked for 12 hours to be fully wetted. 1.5g of sodium periodate, 0.6g of anthraquinone, 0.3g of urea, 0.2g of peregal, 0.2g of sodium polyacrylate and 197.2g of water are added to prepare degumming liquid; mixing the ramie raw ramie short fibers and the degumming reaction solution according to the mass ratio of 1: 10, and taking a 1000mL brown conical flask as a reactor. The pH of the degumming solution is adjusted to 5.0 with 0.1mol/L HCl solution, and the mixture of ramie material and degumming solution is continuously stirred with a magnetic stirrer at a speed of 200rpm in the dark. Heating the water bath to 90 deg.C, maintaining the temperature for 120min, removing colloid from ramie by oxidizing agent, and oxidizing C6 primary hydroxyl group into carboxyl group to obtain 6-carboxyl oxidized cellulose. Soaking the reacted fiber in 0.1mol/L acetone water solution for 1.5h, removing unreacted oxidant, and then washing and soaking the fiber in deionized water for 24 h. Finally, centrifuging and washing for 5 times by adopting a centrifugal machine with the rotating speed of 12000rpm, transferring supernatant liquor into another container, and putting the residual concentrated cellulose suspension into a vacuum freeze dryer; drying at-50 deg.C under 60Pa for 10 hr to obtain powdered oxidized cellulose adsorbent, and storing in a freezing chamber.
4 adult New Zealand rabbits (half of male and female, with a weight of 2.5-3 kg) are selected as experimental animals, pentobarbital sodium solution is injected into ear veins of the experimental rabbits to enable the rabbits to be anesthetized systemically, muscle layers on the backs of the rabbits are cut, and the exposed area is about 2cm multiplied by 2 cm. The obtained oxidized cellulose (area 1cm × 1cm) was spread on the wound surface, and the hemostatic effect was examined. The wound was closed, opened at days 6 and 9 post-test, respectively, and the absorption was observed.
The gum residue ratio of the oxidized cellulose measured by boiling a 20g/L NaOH solution was 2.1%, the crystallinity of the oxidized cellulose measured by an X-ray diffractometer was 62.10%, the Degree of Polymerization (DP) of the oxidized cellulose measured by a Calycol viscosity method was 409, and the carboxyl group content of the oxidized cellulose measured by an acid-base neutralization titration method was 19.0%. The back muscle implantation test of the rabbits shows that the oxidized cellulose can effectively stop bleeding within 100 seconds after being pasted on the wound surface of an animal wound. The oxidized cellulose was partially degraded at day 6 and almost completely degraded at day 9.
Therefore, the method for preparing the oxidized cellulose for hemostasis in the ramie oxidation degumming process provided by the invention has the advantages of small residual gum rate of the prepared oxidized cellulose for hemostasis, moderate crystallinity and polymerization degree, high carboxyl content, high hemostasis speed, stable hemostasis performance and good absorption effect.
Claims (10)
1. A method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie is characterized in that: the method comprises the following 3 steps:
step 1: pretreatment of raw hemp fiber
Pulverizing ramie into short fibers, putting the short fibers into a closed container to balance moisture, and measuring the moisture regain of the short fibers; weighing the mass of the short fiber, and calculating the dry weight of the short fiber according to the moisture regain; adding deionized water into short fibers, and soaking to fully wet and swell the raw hemp cellulose;
step 2: oxidation treatment of cellulose
Preparing degumming reaction liquid from 2-10% of oxidant, 0.5-5% of cellulose protective agent, 0.5-4% of fiber expanding agent, 0.5-3% of surfactant, 0.5-3% of chelating agent and distilled water in percentage by weight; mixing the short fibers of the raw ramie with degumming reaction liquid in a reactor, adjusting the initial pH value of the degumming liquid to 3.0-14.0, putting the reactor into a constant-temperature water bath kettle, stirring the mixture in the reactor under the condition of keeping out of the sun, heating the water bath kettle to 50-100 ℃, preserving the temperature for 40-150 min, fully removing the colloid in the raw ramie by utilizing the oxidability of an oxidant, and oxidizing cellulose with hydroxyl into oxidized cellulose containing a large amount of carboxyl; the residual gum rate of the obtained product is 2.0-2.3%, the polymerization degree is 300-500, and the carboxyl content is 18-22%;
and step 3: washing and stabilizing treatment of oxidized cellulose
Soaking and washing the reacted fiber with an organic solvent to remove unreacted oxidant, and then fully washing and soaking the fiber with deionized water; centrifuging the obtained mixture for layering, transferring supernatant into another container, placing the rest concentrated cellulose suspension into a vacuum freeze-drying instrument, freeze-drying with liquid nitrogen for molding to obtain powdered oxidized cellulose adsorbent, and storing in a freezing chamber.
2. The method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie according to claim 1, characterized in that: in the step 1, the fineness of the crushed short fibers is 20-100 meshes, distilled water is added into the short fibers to enable the mass percentage concentration of the cellulose solids in the distilled water to be 1% -10%, and the soaking time of the distilled water is 12-48 h.
3. The method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie according to claim 1, characterized in that: in the step 2, mixing the ramie raw ramie short fibers and the degumming reaction solution in a mass ratio of 1: 10 in a reactor; adjusting the solution used for adjusting the initial pH value of the degumming solution to be 0.1mol/L NaOH solution or 0.1mol/L HCl solution; the mixture in the reactor was stirred continuously with a magnetic stirrer at a speed of 200 rpm.
4. The method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie according to claim 1, characterized in that: in the step 2, the oxidant is one or more of sodium bromate, sodium chlorate, sodium chlorite, a tetramethylpiperidine oxide-sodium hypochlorite-sodium bromide ternary composite oxidation system, a nitric acid-phosphoric acid-sodium nitrite oxidation system, sodium percarbonate, sodium periodate, potassium periodate, sodium hypochlorite and potassium percarbonate.
5. The method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie according to claim 1, characterized in that: in the step 2, the cellulose protective agent is one or more of sodium benzoate, anthraquinone, magnesium hydroxide, polyvinyl alcohol, water glass, polyacrylamide, magnesium silicate, acetanilide, resorcinol, sodium citrate and sodium benzoate.
6. The method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie according to claim 1, characterized in that: in the step 2, the fiber expanding agent comprises one or two of urea, ethylenediamine, liquid ammonia, thiourea, 4-methylmorpholine-N-oxide, copper ethylenediamine and dimethyl sulfoxide.
7. The method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie according to claim 1, characterized in that: in the step 2, the surfactant is one or two of polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether.
8. The method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie according to claim 1, characterized in that: in the step 2, the metal ion chelating agent comprises one or more of nitrilotriacetic acid, ethylene diamine tetra methylene phosphonic acid sodium, diethylenetriamine penta methylene phosphonic acid, ethylene diamine dipolyphenyl sodium acetate, hydroxy ethylidene diphosphonic acid and sodium salt thereof, sodium polyacrylate and ethylene diamine tetra methylene phosphonic acid sodium.
9. The method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie according to claim 1, characterized in that: in the step 3, the organic solvent used for soaking the fibers after the soaking reaction is one or two of glycerol, ethylene glycol, acetone and 1, 3-propylene glycol, the concentration is 0.1mol/L, and the soaking and washing time is 0.5-2 h.
10. The method for preparing oxidized cellulose for hemostasis in the oxidation degumming process of ramie according to claim 1, characterized in that: in the step 3, the time for fully cleaning and soaking with deionized water is 24 hours; centrifuging and layering the prepared mixture by a centrifuge, wherein the rotating speed of the centrifuge is 6000-12000 rpm, and the centrifuging times are 3-6; the temperature of the freeze drying molding is-40 to-60 ℃, the pressure of the freeze drying molding is 10 to 60Pa, and the time of the freeze drying molding is 4 to 10 hours.
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| CN106894097B (en) * | 2017-03-13 | 2019-09-27 | 东华大学 | A method of ramee is prepared using 2,2,6,6- tetramethyl piperidine -1- oxide radical oxidation system |
| CN107236152B (en) * | 2017-07-07 | 2020-04-21 | 南宁师范大学 | Preparation method of high-strength sisal fiber reinforced cassava starch composite material |
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| CN108485660A (en) * | 2018-03-12 | 2018-09-04 | 大连工业大学 | A kind of preparation method and application of cellulose base N doping fluorescent carbon quantum dot |
| CN112807477B (en) * | 2020-12-30 | 2023-03-07 | 广州迈普再生医学科技股份有限公司 | Composite hemostatic material and preparation method thereof |
| CN114000205B (en) * | 2021-12-06 | 2023-04-04 | 东华大学 | High-quality low-pollution selective oxidation ramie degumming method |
| CN114086262B (en) * | 2021-12-06 | 2023-06-27 | 东华大学 | Oxidative degumming method for ramie using nitrogen hydroxyl phthalimide |
| CN115874440B (en) * | 2022-12-30 | 2023-10-03 | 贵州金玖生物技术有限公司 | Preparation method of water-soluble gauze, product and application thereof |
| CN116375893A (en) * | 2023-03-03 | 2023-07-04 | 贵州金玖生物技术有限公司 | Preparation method of absorbable hemostatic oxidized regenerated cellulose, product and application thereof |
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