CN106466492A - A kind of preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan - Google Patents

Abstract

The invention belongs to biological medicine field of material preparation, it is related to a kind of preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan.First by carboxymethyl chitosan with there is the anionic polyelectrolyte of biocompatibility or polyampholyte is dissolved in deionized water.By reducing the pH value of polyelectrolyte solution, the protonated amino of carboxymethyl chitosan glycan molecule, and with anionic polyelectrolyte or polyampholyte, complex is formed by Coulomb force interaction.After compound polyelectrolyte drying is pulverized, obtain carboxymethyl chitosan polyelectrolyte styptic powder.The styptic powder of the present invention has good biocompatibility and biocidal property, shows excellent hemostatic function.

Description

A kind of preparation method of polyelectrolyte hemostatic powder based on carboxymethyl chitosan

technical field

The invention belongs to the field of biomedical material preparation, and relates to a preparation method of polyelectrolyte hemostatic powder based on carboxymethyl chitosan.

Background technique

Modern medical theory proves that wound healing is a continuous dynamic process of cell-to-cell, cell-to-cell matrix, and soluble media interactions. Wound repair is related to the interaction of local tissue nutrition, microenvironment, growth factor content, microcirculation, hypoxic conditions, infection and other factors, and medical dressings can play a key role. As a main theoretical basis of high-tech medical dressings, the "wet therapy" discovered by British scientists in 1962 believes that when the surface of the wound is maintained in a moist microenvironment, the migration of epithelial cells is significantly accelerated, and the healing speed of the wound is faster than that of wounds. Fast in dry conditions.

Blood is an important substance in the human body. If the bleeding is not stopped in time, it will cause the body to become weak, and a large amount of bleeding will lead to hemorrhagic shock or even death. A hemostatic method that adversely affects the blood circulation of the affected limb during the hemostatic process. The development of wound dressings with rapid hemostasis is a research field that countries all over the world, especially the military, pay close attention to.

There are many types of hemostatic materials in terms of their mechanism of action. For example, hemostatic materials containing fibrinogen, thrombin, etc. directly or indirectly provide external blood coagulation components to accelerate the coagulation process; potato starch, zeolite, etc. make the blood coagulation components concentrate and aggregate through the physical or chemical action of materials to accelerate coagulation; cyanoacrylate, etc. The material has strong adhesion to the tissue, and can directly seal the wound to achieve hemostasis. At present, the main hemostatic materials on the market are BioCer in Germany and Celox Hemostatic King in the UK with chitosan as the main material, PerClot and Arista hemostatic powder in the United States with starch-type absorbable polysaccharide as the main material, and zeolite as the main ingredient in the United States. QuikClot hemostatic powder, WoundStat hemostatic material with montmorillonite as the main material, and TraumaStat, a new hemostatic material combined with mesoporous silicon, chitosan and polyethylene, etc.

The ideal local hemostatic material should have the requirements of rapid hemostasis, mild toxicity and tissue reaction, good biocompatibility, rapid degradation, use, cheap price, accelerated tissue healing, and adaptability to different parts and types of hemorrhage and hemostasis. However, the existing conventional hemostatic methods and hemostatic drugs are far from meeting these requirements. Inorganic hemostatic materials often have certain defects in terms of biological safety. Porous zeolite and potato starch will release a lot of heat after absorbing water in the blood, causing wound tissue damage. Fibrin-based hemostatic materials have poor environmental adaptability, short shelf life and high prices. The polysaccharide hemostatic material with a three-dimensional network structure has a slow water absorption rate and low water absorption rate, and the gel formed after absorbing water has poor viscosity, which cannot effectively block damaged tissues and blood vessels, and the hemostatic effect is not satisfactory.

Chitin widely exists in the shells of marine crustaceans, the inner skeletons of molluscs, insect wings, fungi and algae cell walls. It is a natural polysaccharide and the second largest renewable resource on earth after cellulose. Chitosan is the product of deacetylation of chitin in a strong alkaline solution. It is the only positively charged basic amino polysaccharide that exists in large quantities in natural polysaccharides. It has special physical, chemical and physiological activities, and is non-toxic and biodegradable. , good biocompatibility, is considered to be "the sixth vital element of the human body".

Chitosan is easily soluble in most organic and inorganic acids, but insoluble in water, which limits its range of applications. Carboxymethyl chitosan is the product of carboxymethylation of chitosan. Carboxymethylated products can be divided into O-carboxymethyl chitosan, N-carboxymethyl chitosan and N,O-carboxymethyl chitosan according to the carboxymethyl substitution position. Carboxymethyl chitosan maintains the good safety, non-toxic, harmless, biocompatibility and biodegradability of chitosan, and the introduction of carboxymethyl makes it an amphoteric polymer containing both amino and carboxyl groups. The electrolyte destroys the original crystal structure of chitosan and improves its solubility adaptability. Since the carboxyl and amino groups are both hydrophilic genes, the hydrophilicity of carboxymethyl chitosan is greatly improved, showing strong water absorption and moisturizing properties, film formation, thickening, flocculation, chelation, gelation and emulsification, etc. , are widely used in agriculture, environmental protection, medicine, cosmetics, food processing and other fields.

Carboxymethyl chitosan has been extensively studied as a biomaterial in the medical field. Studies have shown that carboxymethyl chitosan has better antibacterial properties than chitosan in a relatively wide range of substitution degrees. Since carboxymethyl chitosan contains active amino groups and carboxyl groups at the same time, it can be linked with a variety of biologically active substances, and it may become a new generation of targeted and controlled release carrier materials for genes and drugs.

The pKa value of the amino group in the carboxymethyl chitosan molecule is about 6.5. When the pH value of the solution is lower than 6.0, the amino group of the carboxymethyl chitosan molecule is protonated. Therefore, when the pH value of the solution is adjusted between 3.0 and 6.0, the positively charged amino group of the carboxymethyl chitosan molecule can instantaneously form a non-toxic polyanionic electrolyte or amphoteric polyelectrolyte molecule through the Coulomb interaction force. Regular compound. This complex is in a non-equilibrium state, and over time, more stable complexes gradually form through other secondary interactions such as hydrogen bonding, van der Waals forces, charge transfer, and hydrophobic association forces. Utilizing the three-dimensional network structure formed by this polyelectrolyte complex, the use of toxic chemical crosslinking agents such as glutaraldehyde can be avoided in the material preparation process, and the excellent performance of the polyelectrolyte material itself can be better retained. It has important application prospects in the biological field.

Contents of the invention

The object of the present invention is to provide a kind of preparation method of polyelectrolyte hemostatic powder based on carboxymethyl chitosan, the obtained polyelectrolyte hemostatic powder shows excellent hemostatic function, solves the problem that existing conventional hemostatic methods and hemostatic drugs cannot meet the requirements And other issues.

Technical scheme of the present invention is:

A kind of preparation method of polyelectrolyte hemostatic powder based on carboxymethyl chitosan, at first prepare the solution containing carboxymethyl chitosan and anionic polyelectrolyte or amphoteric polyelectrolyte, adjust the pH value of this solution to make carboxymethyl chitosan The sugar amino group is protonated and interacts with anionic polyelectrolyte or amphoteric polyelectrolyte to form a complex through Coulomb force, and the polyelectrolyte complex is dried and pulverized to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder.

The preparation method of the described polyelectrolyte hemostatic powder based on carboxymethyl chitosan, concrete steps are as follows:

1) Prepare an aqueous polyelectrolyte mixture solution containing carboxymethyl chitosan and anionic polyelectrolyte or amphoteric polyelectrolyte, and use NaOH solution to adjust the pH value between 7 and 8;

2) Adjust the pH value of the polyelectrolyte mixture aqueous solution to the range of 3.0 to 6.0, protonate the amino group of the carboxymethyl chitosan molecule, and interact with the anionic polyelectrolyte or amphoteric polyelectrolyte through Coulomb force to form a polyelectrolyte complex;

3) After the polyelectrolyte complex is dried and pulverized, carboxymethyl chitosan polyelectrolyte hemostatic powder is obtained.

The preparation method of the polyelectrolyte hemostatic powder based on carboxymethyl chitosan, step 1) the molecular weight of carboxymethyl chitosan in the polyelectrolyte mixture aqueous solution is 10,000-2,000,000, and the carboxymethyl substitution degree is 30%-120% , the content is 0.1-8wt.% of the total mass of the solution.

The preparation method of polyelectrolyte hemostatic powder based on carboxymethyl chitosan, step 1) the anionic polyelectrolyte or amphoteric polyelectrolyte is a polyelectrolyte with good biocompatibility containing -COO ^- , -SO ³ - , -O- CS ^2- , -O-PO ₃ ^2- natural, semi-synthetic or synthetic organic polymer materials with anionic groups, the content of anionic polyelectrolyte or amphoteric polyelectrolyte is 0.3-20wt.% of the total mass.

In the preparation method of the polyelectrolyte hemostatic powder based on carboxymethyl chitosan, the anionic polyelectrolyte or amphoteric polyelectrolyte used is hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, heparin, sodium alginate , xanthan gum, carrageenan, pectin, gum arabic, karaya gum, tragacanth gum, sodium lignosulfonate, carboxylated starch, carboxymethyl cellulose, polyacrylic acid, polymethacrylic acid, polystyrene sulfonate One or more of acid, polyvinylsulfonic acid, polyvinylphosphonic acid, carboxymethyl chitosan, acrylic acid vinylpyridine copolymer, nucleic acid, and protein.

In the preparation method of the polyelectrolyte hemostatic powder based on carboxymethyl chitosan, step 2) when adjusting the pH value of the polyelectrolyte mixture aqueous solution to the interval of 3.0 to 6.0, adding a proton releasing agent, acidic acid to the polyelectrolyte mixture aqueous solution Solvent or polyelectrolyte mixture aqueous solution is one or two or more of the treatment methods in acidic atmosphere.

In the preparation method of the polyelectrolyte hemostatic powder based on carboxymethyl chitosan, the proton releasing agent adopts gluconolactone, the addition amount is 0.05-5wt.% of the total mass of the polyelectrolyte mixture aqueous solution, and the processing time is 10 minutes to 8 hours; the acidic solution is acidic water or alcohol aqueous solution, using inorganic or organic acids: hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, propanedioic acid Acid, Succinic Acid, Maleic Acid, Tartaric Acid, Benzoic Acid, Phenylacetic Acid, Phthalic Acid, Terephthalic Acid, Valeric Acid, Caproic Acid, Capric Acid, Stearic Acid, Palmitic Acid, Acrylic Acid, Tartaric Acid, Apple Acid, citric acid, ascorbic acid, the treatment time is 0.5 hours to 20 hours; the acidic atmosphere uses hydrochloric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, which are easily volatile inorganic acids or organic acids, and the treatment time is 20 minutes to 18 Hour.

The preparation method of the polyelectrolyte hemostatic powder based on carboxymethyl chitosan, step 3) the polyelectrolyte complex undergoes normal pressure drying, decompression drying, spray drying, fluidized drying, freeze drying, infrared drying, desiccant One or several drying techniques such as drying or microwave drying.

The preparation method of the polyelectrolyte hemostatic powder based on carboxymethyl chitosan, step 3) the dried polyelectrolyte complex passes through pulverizer, ball mill or crusher to refine the particles to obtain carboxymethyl chitosan poly Electrolyte hemostatic powder.

Advantage of the present invention and beneficial effect are:

1. The present invention utilizes the characteristic that carboxymethyl chitosan can dissolve in neutral water to prepare an aqueous solution of polyelectrolyte mixture containing carboxymethyl chitosan and anionic polyelectrolyte or amphoteric polyelectrolyte. By adjusting the pH value of the solution, the amino group of the carboxymethyl chitosan molecule is protonated and positively charged, and interacts with the anionic polyelectrolyte or amphoteric polyelectrolyte in the solution to form a complex through Coulomb force. The compound is dried and pulverized to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder.

2. The present invention utilizes the three-dimensional network structure formed by this polyelectrolyte complex to avoid the use of chemical crosslinking agents (such as glutaraldehyde, etc.) that have certain toxicity, and can better retain polyelectrolyte such as carboxymethyl chitosan. The excellent performance of the electrolyte material itself shows obvious advantages: it has bacteriostasis and excellent hemostatic function; the hemostatic powder has small particles, large specific surface area, strong liquid absorption ability, can quickly absorb water in the blood, concentrate platelets and coagulation factors ; After absorbing water and swelling, it adheres to the wound surface and blocks the broken capillaries of the wound surface; after hemostasis, it forms a hydrogel on the wound surface to provide a good moist environment for the wound and promote wound healing; it is non-irritating to the wound and has good biological properties. Compatibility and biodegradability.

detailed description

In a specific embodiment, the preparation method of polyelectrolyte hemostatic powder based on carboxymethyl chitosan of the present invention, first dissolve carboxymethyl chitosan and biocompatible anionic polyelectrolyte or amphoteric polyelectrolyte in deionized water. By reducing the pH value of the polyelectrolyte mixture aqueous solution, the amino groups of carboxymethyl chitosan molecules are protonated, and interact with anionic polyelectrolytes or amphoteric polyelectrolytes to form complexes through Coulomb force. After the polyelectrolyte complex is dried and pulverized, carboxymethyl chitosan polyelectrolyte hemostatic powder is obtained. The specific steps are:

1) Prepare an aqueous polyelectrolyte mixture solution containing carboxymethyl chitosan and anionic polyelectrolyte or amphoteric polyelectrolyte. _Anionic ^{polyelectrolytes} or ^{amphoteric polyelectrolytes} are natural, semi ^- synthetic or synthetic Organic polymer materials, such as hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, heparin, sodium alginate, carboxymethyl cellulose, xanthan gum, carrageenan, pectin, gum arabic, karaya Gum, Tragacanth Gum (Gumtragacanth), Sodium Lignosulfonate, Carboxylated Starch, Polyacrylic Acid, Polymethacrylic Acid, Polystyrenesulfonic Acid, Polyethylenesulfonic Acid, Polyvinylphosphonic Acid, Carboxymethyl Chitosan One or more of sugar, acrylic acid vinylpyridine copolymer, nucleic acid, protein, etc.;

2) Adjust the pH value of the aqueous solution of the polyelectrolyte mixture to 3.0 to 6.0 by using one or more of the methods of adding a proton-releasing agent, an acidic solvent, or treating the aqueous solution of the polyelectrolyte mixture in an acidic atmosphere. , to protonate the amino groups of carboxymethyl chitosan molecules, and interact with anionic polyelectrolytes or amphoteric polyelectrolytes through Coulomb force to form polyelectrolyte complexes;

3) The polyelectrolyte complex is dried and pulverized to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder.

In order to make the technical solutions and advantages of the present invention clearer, the following will describe in detail in conjunction with specific embodiments.

Example 1

12 grams of carboxymethyl chitosan, 13 grams of sodium polyacrylate and 1 g of gluconolactone were dissolved in 1 liter of deionized water and kept at 50°C for 10 hours. After the polyelectrolyte complex was dried in a blast dryer at 70° C. for 40 hours, it was ball-milled for 1 hour with a ball mill to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The measurement of coagulation index in vitro in this embodiment shows that the coagulation index in vitro is <49%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <95 seconds.

Example 2

12 grams of carboxymethyl chitosan, 10 grams of hyaluronic acid and 1 g of gluconolactone were dissolved in 1 liter of deionized water and kept at 50°C for 10 hours. After the polyelectrolyte complex was dried in a blast dryer at 70° C. for 40 hours, it was ball-milled for 1 hour with a ball mill to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The measurement of coagulation index in vitro in this embodiment shows that the coagulation index in vitro is <65%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <112 seconds.

Example 3

12 grams of carboxymethyl chitosan, 10 grams of hyaluronic acid and 3 grams of gluconolactone were dissolved in 1 liter of deionized water and kept at 50°C for 10 hours. After the polyelectrolyte complex was dried in a blast dryer at 50° C. for 50 hours, it was ball-milled for 1 hour with a ball mill to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The measurement of coagulation index in vitro in this embodiment shows that the coagulation index in vitro is <62%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <120 seconds.

Example 4

12 grams of carboxymethyl chitosan, 12 grams of gum arabic and 1 g of gluconolactone were dissolved in 1 liter of deionized water and kept at 50°C for 10 hours. After the polyelectrolyte complex was dried in a blast dryer at 70° C. for 40 hours, it was ball-milled for 1 hour with a ball mill to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The measurement of coagulation index in vitro in this embodiment shows that the coagulation index in vitro is <70%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <180 seconds.

Example 5

30 grams of carboxymethyl chitosan, 15 grams of sodium alginate and 3 grams of gluconolactone were dissolved in 1 liter of deionized water and kept at 50°C for 10 hours. After the polyelectrolyte complex was dried in a blast dryer at 70° C. for 40 hours, it was ball-milled for 1 hour with a ball mill to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The measurement of coagulation index in vitro in this embodiment shows that the coagulation index in vitro is <44%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <88 seconds.

Example 6

25 grams of carboxymethyl chitosan, 18 grams of carboxylated starch and 1 g of gluconolactone were dissolved in 1 liter of deionized water and kept at 50°C for 10 hours. After the polyelectrolyte complex was dried in a blast dryer at 70° C. for 40 hours, it was ball-milled for 1 hour with a ball mill to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The measurement of coagulation index in vitro in this embodiment shows that the coagulation index in vitro is <55%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <160 seconds.

Example 7

12 grams of carboxymethyl chitosan and 13 grams of sodium polyacrylate were dissolved in 1 liter of deionized water. 10 mL of hydrochloric acid solution (molar concentration 0.1 M) was injected into the polyelectrolyte mixture aqueous solution, and treated at room temperature for 4 hours. After the polyelectrolyte complex was dried in a vacuum oven for 40 hours, it was ball-milled for 1 hour with a ball mill to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The in vitro coagulation index measurement in this example shows that the in vitro coagulation index is <48%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <110 seconds.

Example 8

12 grams of carboxymethyl chitosan and 13 grams of sodium polyacrylate were dissolved in 1 liter of deionized water, then put into an acetic acid atmosphere and treated at room temperature for 8 hours. After the polyelectrolyte complex was dried in a blast dryer at 70° C. for 40 hours, it was ball-milled for 1 hour with a ball mill to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The measurement of coagulation index in vitro in this embodiment shows that the coagulation index in vitro is <46%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <110 seconds.

Example 9

19 grams of carboxymethyl chitosan and 18 grams of carboxymethyl cellulose were dissolved in 1 liter of deionized water, and then put into an acetic acid atmosphere. Treat for 8 hours at room temperature. After the polyelectrolyte complex was dried in a blast dryer at 70° C. for 40 hours, it was ball-milled for 1 hour with a ball mill to obtain carboxymethyl chitosan polyelectrolyte hemostatic powder. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The measurement of coagulation index in vitro in this embodiment shows that the coagulation index in vitro is <47%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <150 seconds.

Example 10

12 grams of carboxymethyl chitosan was dissolved in 500 mL of distilled water. 13 grams of sodium polyacrylate was dissolved in 400 mL of distilled water. 5g of gluconolactone was dissolved in 100mL of distilled water. Combine carboxymethyl chitosan, sodium polyacrylate and gluconolactone solutions, and keep warm at 50°C for 10 hours. After the polyelectrolyte complex was dried in an infrared dryer for 48 hours, the carboxymethyl chitosan polyelectrolyte hemostatic powder was obtained by ball milling for 1 hour. The hemostatic powder has good biocompatibility and antibacterial property, and exhibits excellent hemostatic function. The measurement of coagulation index in vitro in this embodiment shows that the coagulation index in vitro is <54%; the hemostatic effect test result of the rabbit ear artery bleeding model shows that the hemostatic time is <105 seconds.

Claims (9)

1. a kind of preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan it is characterised in that：First Prepare the solution containing carboxymethyl chitosan and anionic polyelectrolyte or polyampholyte, adjust this solution PH value makes carboxymethyl chitosan protonated amino and passes through coulomb with anionic polyelectrolyte or polyampholyte Power interacts and forms complex, and compound polyelectrolyte drying obtains carboxymethyl chitosan and gathers electrolysis after pulverizing Matter styptic powder.

2. the preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan according to claim 1, It is characterized in that, comprise the following steps that：

1) polyelectrolyte containing carboxymethyl chitosan and anionic polyelectrolyte or polyampholyte for preparation mixing Thing aqueous solution, polyelectrolyte mixtures aqueous solution NaOH solution reconciles pH value between 7～8；

2) pH value adjusting polyelectrolyte mixtures aqueous solution is interval to 3.0～6.0, makes carboxymethyl chitosan sugar The protonated amino of son, is interacted by Coulomb force with anionic polyelectrolyte or polyampholyte, is formed Compound polyelectrolyte；

3), after compound polyelectrolyte drying is pulverized, obtain carboxymethyl chitosan polyelectrolyte styptic powder.

3. the preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan according to claim 2, It is characterized in that, step 1) in polyelectrolyte mixtures aqueous solution carboxymethyl chitosan molecular weight 10000～ 2000000, degree of substitution by carboxymethyl is 30%～120%, and content is 0.1～8wt.% of described solution gross mass.

4. the preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan according to claim 2, It is characterized in that, step 1) anionic polyelectrolyte or polyampholyte be to have good biocompatibility Contain-COO^-、-SO^3-、-O-CS^2-、-O-PO₃ ^2-Anionic group natural, semi-synthetic or synthesis organic high The content of molecular material, anionic polyelectrolyte or polyampholyte is 0.3～20wt.% of described gross mass.

5. the preparation side of the polyelectrolyte styptic powder based on carboxymethyl chitosan according to claim 2 or 4 Method is it is characterised in that the anionic polyelectrolyte adopting or polyampholyte are hyaluronic acid, chondroitin sulfate Element, dermatan sulfate, keratan sulfate, heparin, sodium alginate, xanthan gum, carrageenan, pectin, I Uncle's natural gum, POLY-karaya, tragacanth gum, sodium lignin sulfonate, Carboxylic Derivates of Starch, carboxymethyl cellulose, polypropylene Acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinyl sulfonic acid, polyvinylphosphonic acid, carboxymethyl chitosan, One of vinyl pyridine copolymer, nucleic acid, protein or two or more.

6. the preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan according to claim 2, It is characterized in that, step 2) adjust the pH value of polyelectrolyte mixtures aqueous solution to 3.0～6.0 interval when, adopt Add proton release agent, acid flux material or polyelectrolyte mixtures water-soluble in polyelectrolyte mixtures aqueous solution Liquid one of processing method or two or more in acid atmosphere.

7. the preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan according to claim 6, It is characterized in that,

Proton release agent adopts gluconic acid lactone, and addition is polyelectrolyte mixtures aqueous solution gross mass 0.05～5wt.%, process time is 10 minutes to 8 hours；

Acid solution is water or the alcohol-water solution of acid, using mineral acid or organic acid：Hydrochloric acid, sulphuric acid, phosphoric acid, Nitric acid, formic acid, acetic acid, propanoic acid, butanoic acid, octanoic acid, adipic acid, ethanedioic acid, malonic acid, succinic acid, horse Come sour, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, p-phthalic acid, valeric acid, caproic acid, capric acid, Stearic acid, palmitic acid, acrylic acid, tartaric acid, malic acid, citric acid, ascorbic acid, process time is 0.5 Hour was to 20 hours；

Acid atmosphere using hydrochloric acid, nitric acid, formic acid, acetic acid, propanoic acid, ethanedioic acid be easy to the mineral acid that volatilizees or Organic acid, process time is 20 minutes to 18 hours.

8. the preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan according to claim 2, It is characterized in that, step 3) compound polyelectrolyte is through constant pressure and dry, drying under reduced pressure, spray drying, stream Change one of dry technologies such as drying, lyophilization, infrared drying, desiccant dryness or microwave drying or Several dryings.

9. the preparation method of the polyelectrolyte styptic powder based on carboxymethyl chitosan according to claim 2, It is characterized in that, step 3) dried compound polyelectrolyte makes through pulverizer, ball mill or disintegrating machine Grain refine, obtains carboxymethyl chitosan polyelectrolyte styptic powder.