CN114316347A - Polyacrylic acid/chitosan ultra-large pore low-temperature sponge and preparation method and application thereof - Google Patents
Polyacrylic acid/chitosan ultra-large pore low-temperature sponge and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyacrylic acid/chitosan ultra-large pore low-temperature sponge, a preparation method and application thereof, wherein the polyacrylic acid/chitosan ultra-large pore low-temperature sponge comprises 1-20 wt% of raw material component acrylic acid; 0.5-10 wt% of chitosan; the cross-linking agent is 1.1-86 wt% of acrylic acid; the initiator is 0.035 to 10.5 weight percent of acrylic acid; the reducing agent is 0.03-9.5 wt% of acrylic acid; and the balance water. Initiating low-temperature polymerization of chitosan and acrylic acid monomer at 0 ℃ under the conditions of a cross-linking agent, an initiator and a reducing agent to form a frozen solvent crystal and an unfrozen liquid-phase micro-phase, wherein the solvent grows to the periphery in the icing process to form continuous crystals, the polymerized monomer is concentrated in the liquid-phase micro-phase, a continuous hole wall is formed through polymerization reaction, and interconnected macropores are formed through unfreezing at room temperature; the chitosan chain and the polyacrylic acid chain form a semi-interpenetrating network through the interaction of static electricity and hydrogen bonds, and finally the low-temperature hemostatic sponge with super-large pores and rapid absorption is obtained.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a polyacrylic acid/chitosan super-macroporous low-temperature sponge and a preparation method and application thereof.
Background
Uncontrolled or massive bleeding from accidental trauma or surgery remains a significant life-threatening concern, with most patients occurring prior to hospitalization, and it is therefore important to find an effective hemostatic agent to control bleeding. An ideal hemostatic agent should not only have good biocompatibility, be able to effectively control bleeding, but also be convenient to use, convenient and fast, low in cost, and free of toxic and side effects. Although the hemostatic agents commonly available on the market, such as cyanoacrylate, gelatin-based hemostatic sponge or bandage, chitosan-based hemostatic sponge, fibrin-based hemostatic agent, and zeolite, have good hemostatic effects, they are severely limited in controlling arterial bleeding, visceral bleeding, incompressible bleeding, and major bleeding due to cost problems, poor applicability, and potential toxic and side effects. Therefore, it is extremely important to develop a hemostatic agent that is low in cost, easy to use, and capable of effectively controlling bleeding.
Chitosan is widely used in the biomedical field because of its good biocompatibility, biodegradability, wound healing acceleration, anti-infection, non-toxicity, low cost, antimicrobial activity. Particularly, chitosan has abundant active amino groups, has positive surface, can interact with red blood cells and platelets with negative points, and enables the red blood cells and the platelets to be adhered and activated in large quantity without depending on a blood coagulation mechanism, thereby being widely applied to hemostatic agents. However, chitosan itself is poor in mechanical properties and absorption properties and unstable, and how to solve the above problems has been the main direction of current research.
Disclosure of Invention
The invention aims to provide a polyacrylic acid/chitosan ultra-large pore low-temperature sponge, a preparation method and application thereof.
In order to achieve the above object, as an aspect of the present invention, there is provided a polyacrylic acid/chitosan ultra-large pore low temperature sponge, comprising the following raw material components by weight: 1-20 wt% of acrylic acid; 0.5-5 wt% of chitosan; the content of the cross-linking agent is 1.1 to 86 weight percent of the acrylic acid, and the content of the initiator is 0.035 to 10.5 weight percent of the acrylic acid; the content of the reducing agent is 0.03-9.5 wt% of the acrylic acid; and the balance water.
According to the invention, the polyacrylic acid/chitosan ultra-large pore low-temperature sponge comprises the following raw material components in percentage by weight: 3-15 wt% of acrylic acid; 0.5-3 wt% of chitosan; the content of the cross-linking agent is 10-50 wt% of acrylic acid; the content of the initiator is 0.35 to 6.5 weight percent of the acrylic acid; the content of the reducing agent is 0.3-6 wt% of the acrylic acid; and the balance water.
Preferably, the polyacrylic acid/chitosan ultra-large pore low-temperature sponge comprises the following raw material components in percentage by weight: 5-10 wt% of acrylic acid; 1.0-2.0 wt% of chitosan; the content of the cross-linking agent is 20-45 wt% of the acrylic acid; the content of the initiator is 1.05-5 wt% of the acrylic acid; the content of the reducing agent is 0.95-5 wt% of the acrylic acid; and the balance water.
According to the invention, the crosslinking agent is N, N' -methylenebisacrylamide; the initiator is selected from ammonium persulfate and/or potassium persulfate; the reducing agent is selected from one or more of potassium metabisulfite, sodium bisulfite and sodium thiosulfate.
According to another aspect of the invention, the preparation method of the polyacrylic acid/chitosan super-macroporous low-temperature sponge comprises the following steps: 1) preparing a chitosan acetic acid aqueous solution, dissolving chitosan in the acetic acid aqueous solution, and obtaining a chitosan acetic acid uniform solution under the condition of magnetic stirring. 2) Dropwise adding an acrylic acid monomer into the chitosan acetic acid homogeneous solution prepared in the step 1), and proportionally adding a cross-linking agent N, N' -methylene bisacrylamide to obtain a homogeneous solution. 3) Adding an initiator and a reducing agent into the uniform solution obtained in the step 2) in proportion, supplementing water to the balance, magnetically stirring, uniformly mixing, transferring the solution into a low-temperature environment below 0 ℃, initiating a free radical polymerization reaction to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the polyacrylic acid/chitosan ultra-macroporous low-temperature sponge.
According to the invention, the crosslinking agent is N, N' -methylenebisacrylamide; the initiator is selected from one or more of ammonium persulfate and/or potassium persulfate; preferably ammonium persulfate; the reducing agent is selected from one or more of potassium metabisulfite, sodium bisulfite and sodium thiosulfate; potassium metabisulfite is preferred.
According to the invention, in the homogeneous solution obtained in step 2), the acrylic acid content is between 1 and 20 wt%; the content of the chitosan is 0.5-5 wt%; the content of the added crosslinking agent N, N' -methylene-bisacrylamide is 1.1-86 wt% of the acrylic acid.
Preferably, the content of the acrylic acid is 5-10 wt%; the content of the chitosan is 1-5 wt%; the content of the added cross-linking agent N, N' -methylene-bisacrylamide is 20-45 wt% of the acrylic acid.
According to the invention, the initiator added in step 3) is present in an amount of 0.035 to 10.5 wt.% with respect to the acrylic acid; the content of the reducing agent added is 0.03 to 9.5 wt% of the acrylic acid.
Preferably, the content of the initiator added in the step 3) is 1.05-5 wt% of acrylic acid; the content of the reducing agent added is 0.95 to 5 wt% of the acrylic acid. Preferably, the balance of water is controlled to be 3 to 15 wt% of the solid content.
According to the invention, the concentration of the acetic acid aqueous solution is 0.5-1.5 v/v%; preferably 1 v/v%; the concentration of the chitosan acetic acid homogeneous aqueous solution prepared in the step 1) is 0.5-3.5 wt%; preferably 1.5 wt% to 2.5 wt%; for example, it may be 1.5 wt%, 1.6 wt%, 1.8 wt%, 2.0 wt%, 2.2 wt%, or 2.5 wt%.
According to the invention, in the step 3), magnetic stirring is carried out for 1-20 minutes, the solution is poured into a mould after uniform mixing, and the mould is moved into an environment with the temperature of-40-0 ℃ for polymerization reaction for 6-72 hours.
According to another aspect of the invention, the application of the polyacrylic acid/chitosan super-macroporous low-temperature sponge in arterial hemostasis and body surface hemostasis is further provided.
The invention has the beneficial effects that:
the invention takes acrylic acid and chitosan as raw materials, adopts a low-temperature structuring method to carry out free radical polymerization, takes ice crystals as pore-forming agents, forms the ultra-macroporous low-temperature sponge with a large number of continuous micron-sized pores, has the characteristic of quick absorption, improves the hemostasis efficiency, has the advantages of easily obtained raw materials, low cost, simple operation and the like, and can be recycled. The invention takes polyacrylic acid as a bracket material, greatly improves the hydrophilicity and the mechanical stability of the ultra-large pore low-temperature sponge, and takes chitosan as a material, and has more excellent hemostatic effect because the surface of the chitosan has rich active amino groups. The swelling rate of the super-macroporous low-temperature sponge prepared by the method can reach 1600%, the time for reaching swelling equilibrium is less than 5s, the super-macroporous low-temperature sponge has high porosity (more than 85%), even 98.9% and high blood absorption capacity (more than 1000%), and the super-macroporous low-temperature sponge can be repeatedly used, and can still keep a complete shape after being circulated for 10 times.
Drawings
FIGS. 1a and 1b are optical photographs of the super-macroporous cryogenic sponge prepared in example 1 of the present invention;
fig. 2a and 2b are SEM images of the ultra-large pore cryogenic sponge prepared in example 1 of the present invention.
FIG. 3 is a graph showing the swelling ratio of the ultra-large pore low temperature sponge prepared in example 1 of the present invention.
FIG. 4 is a graph of whole blood clotting time for the ultra large pore cryosponge prepared in example 1 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention, but the invention can be practiced in many different ways, as defined and covered by the claims.
The ultra-large pores in the ultra-large pore low temperature sponge in the invention mean that the pore size is larger than 100 μm.
In order to solve the problems of poor mechanical property and absorbability, instability and the like of the conventional hemostatic, the invention provides a polyacrylic acid/chitosan super-macroporous low-temperature sponge which is characterized by comprising the following raw materials in percentage: 1-20 wt% of acrylic acid; 0.5-5 wt% of chitosan; the content of the cross-linking agent is 1.1-86 wt% of acrylic acid; the content of the initiator is 0.035 to 10.5 weight percent of the acrylic acid; the content of the reducing agent is 0.03-9.5 wt% of acrylic acid, and the balance is water.
Preferably, the polyacrylic acid/chitosan super-macroporous low-temperature sponge comprises the following raw materials in percentage by weight: 3-15 wt% of acrylic acid; 0.5-3 wt% of chitosan; the content of the cross-linking agent is 10-50 wt% of acrylic acid; the content of the initiator is 0.35 to 6.5 weight percent of the acrylic acid; the content of the reducing agent is 0.3-6 wt% of the acrylic acid; and the balance water.
The cross-linking agent adopted in the invention is N, N' -methylene bisacrylamide; the initiator is selected from ammonium persulfate and/or potassium persulfate; the reducing agent is selected from one or more of potassium metabisulfite, sodium bisulfite and sodium thiosulfate. The N, N' -methylene bisacrylamide is adopted as a crosslinking agent, is mainly considered as a double-bond polymerization crosslinking agent, and has the characteristics of high reaction activity and low cost.
The invention adopts ammonium sulfate and/or potassium persulfate as the initiator, because the initiator is easy to dissolve in water, has stronger oxidability and higher initiation efficiency.
The invention adopts potassium metabisulfite, sodium bisulfite or sodium thiosulfate as reducing agents, not only can be used in combination with ammonium persulfate or potassium persulfate and the like due to strong reducibility, but also can greatly reduce the activation energy, and has the characteristics of low polymerization temperature and high polymerization rate.
By adopting the technical scheme, the invention adopts acrylic acid and chitosan as raw materials, adopts a low-temperature structuring method to carry out free radical polymerization, adopts ice crystals as pore-forming agents to obtain the ultra-macroporous low-temperature sponge with a large number of continuous micron-sized pores, has the characteristics of quick absorption and hemostasis, improves the hemostasis efficiency, and has the advantages of easily obtained raw materials, low cost, simple operation and the like, and can be recycled.
The invention takes polyacrylic acid as a bracket material, greatly improves the hydrophilicity and the mechanical stability of the ultra-macroporous low-temperature sponge because the polyacrylic acid has the characteristics of high hydrophilicity, high absorption rate, good mechanical property and the like, and has more excellent hemostatic effect because the surface of the chitosan which is taken as a material has rich active amino groups. The swelling rate of the super-macroporous low-temperature sponge prepared by the method can reach 1600%, the time for reaching swelling equilibrium is less than 5s, the super-macroporous low-temperature sponge has high porosity (more than 85%), even 98.9% and high blood absorption capacity (more than 1000%), and the super-macroporous low-temperature sponge can be repeatedly used, and can still keep a complete shape after being circulated for 10 times.
According to another aspect of the invention, the preparation method of the polyacrylic acid/chitosan super-macroporous low-temperature sponge comprises the following steps:
1) preparing a chitosan acetic acid aqueous solution, dissolving chitosan in the acetic acid aqueous solution, and obtaining a chitosan acetic acid uniform solution under the condition of magnetic stirring. The concentration of the acetic acid aqueous solution is 0.5-1.5 v/v%, for example, the acetic acid aqueous solution is dissolved in 1 v/v% acetic acid aqueous solution, and 2 wt% chitosan acetic acid homogeneous solution is obtained.
2) Dropwise adding an acrylic acid monomer into the chitosan acetic acid homogeneous solution prepared in the step 1), and proportionally adding a cross-linking agent N, N' -methylene bisacrylamide to obtain a homogeneous solution.
3) Adding an initiator and a reducing agent into the uniform solution obtained in the step 2) in proportion, supplementing water to the balance, magnetically stirring, uniformly mixing, transferring the solution into a low-temperature environment below 0 ℃, initiating a free radical polymerization reaction to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the polyacrylic acid/chitosan ultra-macroporous low-temperature sponge.
The cross-linking agent is N, N' -methylene bisacrylamide; the initiator is selected from one or more of ammonium persulfate and/or potassium persulfate; preferably ammonium persulfate; the reducing agent is selected from one or more of potassium metabisulfite, sodium bisulfite and sodium thiosulfate; potassium metabisulfite is preferred.
The concentration of the chitosan acetic acid homogeneous aqueous solution prepared in the step 1) is 0.5-3.5 wt%; preferably 1.5 wt% to 2.5 wt%; for example, it may be 1.5 wt%, 1.6 wt%, 1.8 wt%, 2.0 wt%, 2.2 wt%, or 2.5 wt%.
In a preferred embodiment of the present invention, the acrylic acid content in the homogeneous solution obtained in step 2) is 1 to 20% by weight; the content of chitosan is 0.5-5 wt%; the content of the added cross-linking agent is 1.1-86 wt% of acrylic acid. More preferably, the acrylic acid content is 3 to 15 wt%; the content of chitosan is 0.5-3 wt%; the content of the added cross-linking agent N, N' -methylene-bisacrylamide is 10-50 wt% of the acrylic acid.
Preferably, the acrylic acid content is 5-10 wt%; the content of the chitosan is 1-5 wt%; the content of the added cross-linking agent N, N' -methylene-bisacrylamide is 20-45 wt% of the acrylic acid.
The content of the acrylic acid is controlled within the range, the factors such as crosslinking density, mechanical strength and the like are mainly considered, the acrylic acid in the product mainly improves the mechanical strength and strong hydrophilicity to promote absorption, the generated polyacrylic acid is used as a scaffold material, if the content of the acrylic acid is low, the crosslinking density is too low to support the mechanical strength of the material, if the content of the acrylic acid is too high, the crosslinking density is too high, the elasticity or toughness of the material is reduced, the compression resistance and the repeated use of the material are not facilitated, and the material is not suitable for clinical application.
Preferably, the content of the initiator added in the step 3) is 0.035 to 10.5 wt% of acrylic acid; the content of the reducing agent added is 0.03 to 9.5 wt% of the acrylic acid. More preferably, the content of the initiator added in the step 3) is 0.35 to 6.5 wt% of acrylic acid; the reducing agent is 0.3-6 wt% of acrylic acid.
Further preferably, the content of the initiator added in the step 3) is 1.05-5 wt% of acrylic acid; the content of the added reducing agent is 0.95-5 wt% of the acrylic acid.
The content of the initiator is controlled mainly by considering molecular weight, initiation rate and mechanical strength, if the content of the initiator is too high, too many free radicals can be caused, the initiation rate is accelerated, the molecular weight is reduced, a molecular chain is shortened, the brittleness of the material is increased, too low, too few free radicals can be caused, the initiation is incomplete, the initiation rate is reduced, and the mechanical strength is weak; if the content of the reducing agent is too high, the reaction is too fast and uneven; too low easily causes problems such as incomplete reaction. Comprehensively, the invention takes the content of acrylic acid as a reference, controls the adding amount of the initiator and the reducing agent in the range, mainly considers that the initiator and the reducing agent of a redox initiation system need to be matched for use, not only can reduce the decomposition activation energy of peroxide and initiate the polymerization of monomers under the condition of lower temperature, but also can increase the decomposition rate of the peroxide, thereby increasing the polymerization rate.
Preferably, the balance of water is controlled to be 3 wt% to 15 wt% of the solid content.
According to the invention, in the step 3), the solution is magnetically stirred for 1-20 minutes, and after the solution is uniformly mixed, the solution is poured into a mold and is transferred into an environment with the temperature of-40-0 ℃ for polymerization reaction for 6-72 hours.
The invention combines chitosan with good biocompatibility and hemostatic property with polyacrylic acid with good hydrophilicity, high absorbability and excellent mechanical property; dissolving chitosan in an acetic acid solution to form a uniform solution, uniformly dispersing an acrylic monomer in the chitosan solution, and initiating free radical polymerization under the action of a cross-linking agent, an initiator and a reducing agent; then the whole system is placed below 0 ℃ to initiate low-temperature polymerization, when the temperature is lower than the freezing point of the solvent, thermally induced phase separation can be caused, frozen solvent crystals and unfrozen liquid-phase micro-phases are formed, the solvent continuously grows to the periphery in the freezing process to gradually form a continuous crystal structure serving as a pore-forming agent, the polymerization monomer is continuously concentrated in the liquid-phase micro-phases, and the polymerization reaction is continued to form continuous pore walls; after thawing at room temperature, forming interconnected macropores; the chitosan chains and the polyacrylic acid chains form a semi-interpenetrating network through electrostatic interaction and hydrogen bonding interaction. Because of the stable mechanical property and good hydrophilicity of polyacrylic acid and the low-temperature polymerized ice crystals serving as pore-forming agents, the low-temperature hemostatic sponge with super large pores, quick absorption and effective hemostasis is formed under the synergistic effect of the superior hemostatic effect of chitosan.
The invention also provides application of any polyacrylic acid/chitosan super-macroporous low-temperature sponge in artery hemostasis and body surface hemostasis.
The technical scheme of the invention is further explained by combining specific examples.
The reagents used in the following examples include essentially the following: chitosan (CS), Acrylic Acid (AA), N, N' -Methylene Bisacrylamide (MBA), Ammonium Persulfate (APS), potassium metabisulfite (K)2S2O5) Deionized water (DIW).
Example 1
1) Preparing 5ml of 2 wt% chitosan acetic acid aqueous solution: 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and a 2 wt% chitosan homogeneous solution is obtained under the condition of magnetic stirring.
2) 0.05g of acrylic acid is added dropwise to the homogeneous chitosan solution obtained in step 1), and 0.0215g of cross-linking agent N, N' -methylenebisacrylamide is added in proportion to obtain a homogeneous solution. Wherein, the content of acrylic acid is 5 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 45 wt% of acrylic acid.
3) Adding 0.0025g of initiator ammonium persulfate and 0.00225g of reducing agent potassium metabisulfite into the uniform solution obtained in the step 2), supplementing water in balance, controlling the balance to be 3 wt% of solid content, magnetically stirring for 5min, and uniformly mixing. The initiator content added is 5 wt% of acrylic acid; the reducing agent was added in an amount of 5 wt% based on the acrylic acid.
4) Pouring the solution obtained in the step 3) into a mould, transferring the mould into an environment with the temperature of minus 20 ℃, initiating polymerization for 24 hours, and freeze-drying the obtained low-temperature gel to obtain the low-temperature super-macroporous sponge.
Fig. 1a and 1b are optical photographs of the ultra-large pore low temperature sponge prepared in example 1, and it can be seen that it has a stable and white sponge-like structure.
Fig. 2a and 2b are SEM images of the ultra-macroporous cryogenic sponge prepared in example 1, and it can be seen that a large number of continuous micro-sized macropores are formed, the pore wall is smooth, the pore diameter is greater than 100 μm, and the pore diameter is uniform, which indicates that the ultra-macroporous cryogenic sponge has the characteristic of rapid absorption and improves the hemostatic efficiency.
The hydrophilic property and the mechanical stability of the super-macroporous low-temperature sponge are tested, the swelling multiplying power of the super-macroporous low-temperature sponge prepared in the example 1 is tested by a hydrometer method to verify the water absorption rate, as shown in fig. 3 and fig. 4, the swelling multiplying power of PAA (polyacrylic acid) is 2250%, and the super-macroporous low-temperature sponge (PAA) prepared by the method is provided with the super-macroporous low-temperature sponge (PAA)7/CS、PAA5/CS、PAA3CS) exceeds 1500% and even up to 2142%. The low-temperature super-macroporous sponge can quickly swell and balance (<5s), wherein the control group is polyacrylic acid PAA polymerized at normal temperature.
The porosity of the ultra-large pore low-temperature sponge is tested by a density method, and the porosity is high, namely 97.9 percent.
The blood absorption capacity of the ultra-large pore low-temperature sponge is tested by adopting a weighing method, the ultra-large pore low-temperature sponge has higher blood absorption capacity (> 1000%), can be repeatedly used, and can still keep a complete shape after 10 times of circulation.
After the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 2
1) Preparing 5ml of 2 wt% chitosan acetic acid aqueous solution: 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, a 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step 1), and 0.215g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. Wherein, the content of acrylic acid is 10 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 43 wt% of acrylic acid.
3) Adding 0.025g of initiator ammonium persulfate and 0.0225g of reducing agent potassium metabisulfite into the uniform solution obtained in the step 2), supplementing water in balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein, the content of the added initiator is 5 wt% of the acrylic acid; the content of the reducing agent added was 4.5% by weight of acrylic acid.
4) Pouring the solution obtained in the step 3) into a mold, transferring the mold into an environment with the temperature of-20 ℃, initiating a free radical polymerization reaction for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The hydrophilic performance and the mechanical stability of the low-temperature super-macroporous sponge are tested by the same test method as in example 1, the swelling ratio of the low-temperature super-macroporous sponge is 2254%, the swelling balance can be rapidly realized, the swelling balance time is less than 5s, the porosity is as high as 94%, the pore diameter is as large as 150 microns, the sponge can be repeatedly used, and the shape can still be kept intact after 10 times of circulation. After 80% strain of uniaxial compression test, the low-temperature super-macroporous sponge can still keep complete shape and still has good structural integrity after 100 compression cycles.
Example 3
1) 5ml of 2 wt% chitosan acetic acid aqueous solution is prepared, 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and a 2 wt% chitosan uniform solution is obtained under the condition of magnetic stirring.
2) 1g of acrylic acid was added dropwise to the homogeneous solution of step 1), and 0.43g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. Wherein, the content of acrylic acid is 20 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 43 wt% of acrylic acid.
3) Adding 0.05g of initiator ammonium persulfate and 0.045g of reducing agent potassium metabisulfite into the uniform solution obtained in the step 2), supplementing water in balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein, the content of the added initiator is 5 wt% of the acrylic acid; the content of the reducing agent added was 4.5% by weight of acrylic acid.
4) Pouring the solution obtained in the step 3) into a mold, transferring the mold into an environment with the temperature of-20 ℃, initiating free radical polymerization reaction for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The hydrophilic performance and the mechanical stability of the low-temperature super-macroporous sponge are tested by the same test method as in example 1, the swelling ratio of the low-temperature super-macroporous sponge is 1950%, the low-temperature super-macroporous sponge can be quickly swelled and balanced, the swelling balance time is less than 5s, the porosity is as high as 94%, the pore diameter is as large as 150 microns, the low-temperature super-macroporous sponge can be repeatedly used, and the complete shape can be still kept after 10 times of circulation.
After 80% strain of uniaxial compression test, the low-temperature super-macroporous sponge can still keep complete shape and still has good structural integrity after 100 compression cycles.
Example 4
1) Preparing 5ml of 0.5 wt% chitosan acetic acid aqueous solution, dissolving 0.025g of chitosan in 1 v/v% acetic acid aqueous solution, and obtaining 0.5 wt% chitosan uniform solution under the condition of magnetic stirring.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step 1), and 0.215g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. The acrylic acid content was 10 wt%; the content of the chitosan is 0.5 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 43 wt% of acrylic acid.
3) Adding 0.025g of initiator ammonium persulfate and 0.0225g of reducing agent potassium metabisulfite into the uniform solution obtained in the step 2), supplementing water in balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein the content of the added initiator is 5 wt% of the acrylic acid, and the content of the added reducing agent is 4.5 wt% of the acrylic acid.
4) Pouring the solution obtained in the step 3) into a mold, transferring the mold into an environment with the temperature of-20 ℃, initiating free radical polymerization reaction for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The hydrophilic performance and the mechanical stability of the low-temperature super-macroporous sponge are tested by the same test method as in example 1, the swelling rate of the low-temperature super-macroporous sponge is 2246 percent, the low-temperature super-macroporous sponge can be quickly swelled and balanced, the swelling balance time is less than 5s, the porosity is as high as 96.2 percent, the pore diameter is 155 mu m, the sponge can be repeatedly used, and the shape can still be kept intact after 10 times of circulation. After 80% strain of uniaxial compression test, the low-temperature super-macroporous sponge can still keep complete shape and still has good structural integrity after 100 compression cycles.
Example 5
1) 5ml of 5 wt% chitosan acetic acid aqueous solution is prepared, 0.25g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and a 5 wt% chitosan uniform solution is obtained under the condition of magnetic stirring.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step 1), and 0.215g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. The acrylic acid content was 10 wt%; the content of the chitosan is 5 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 43 wt% of acrylic acid.
3) Adding 0.025g of initiator ammonium persulfate and 0.0225g of reducing agent potassium metabisulfite into the uniform solution obtained in the step 2), supplementing water in balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein, the content of the added initiator is 5 wt% of the acrylic acid; the content of the reducing agent added was 4.5% by weight of acrylic acid.
4) Pouring the solution obtained in the step 3) into a mould, transferring the mould into an environment with the temperature of-20 ℃, initiating polymerization for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling ratio of the super-macroporous low-temperature sponge is 2110%, the swelling equilibrium time is less than 5s, the porosity is as high as 95.7%, the super-macroporous low-temperature sponge can be repeatedly used, and the super-macroporous low-temperature sponge can still keep a complete shape after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and a water absorption rate test shows that the low-temperature super-macroporous sponge can be rapidly swelled and balanced (<5s), and after the strain of a uniaxial compression test is 80%, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 6
1) 5ml of 2 wt% chitosan acetic acid aqueous solution is prepared, 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution in step (1), and 0.0055g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. The acrylic acid content was 10 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 1.1 wt% of acrylic acid.
3) And (3) adding 0.025g of initiator ammonium persulfate and 0.0225g of reducing agent potassium metabisulfite into the uniform solution obtained in the step (2), supplementing water to the balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein, the content of the added initiator is 5 wt% of the acrylic acid; the content of the reducing agent added was 4.5% by weight of acrylic acid.
4) And (4) pouring the solution obtained in the step (3) into a mold, and transferring the mold into an environment with the temperature of-20 ℃ to initiate polymerization for 24 hours. Forming polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling ratio of the low-temperature super-macroporous sponge is 2009%, the time for reaching swelling balance is less than 5s, the porosity is as high as 94.5%, the sponge can be repeatedly used, and the complete shape can be still kept after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and the water absorption rate test shows that the low-temperature super-macroporous sponge can be quickly swelled and balanced (<5 s); after the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 7
1) 5ml of 2 wt% chitosan acetic acid aqueous solution is prepared, 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step (1), and 0.43g of N, N' -methylenebisacrylamide as a crosslinking agent was added in proportion to obtain a homogeneous solution. The acrylic acid content was 10 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 86 wt% of acrylic acid.
3) Adding 0.025g of initiator ammonium persulfate and 0.0225g of reducing agent potassium metabisulfite into the uniform solution obtained in the step 2), magnetically stirring for 5min, and uniformly mixing. Supplementing water to the balance, wherein the balance is controlled to be 5 wt% of the solid content, and the content of the added initiator is 5 wt% of that of acrylic acid; the content of the reducing agent added was 4.5% by weight of acrylic acid.
4) Pouring the solution obtained in the step 3) into a mould, transferring the mould into an environment with the temperature of-20 ℃, initiating polymerization for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling ratio of the low-temperature super-macroporous sponge is 1950%, the time for reaching swelling equilibrium is less than 5s, the porosity is as high as 96.1%, the sponge can be repeatedly used, and the complete shape can be still kept after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and the water absorption rate test shows that the low-temperature super-macroporous sponge can be quickly swelled and balanced (<5 s); after the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 8
1) 5ml of 2 wt% chitosan acetic acid aqueous solution is prepared, 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step 1), and 0.215g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. The acrylic acid content was 10 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 43 wt% of acrylic acid.
3) 0.000175g of initiator ammonium persulfate and 0.00015g of reducing agent potassium metabisulfite are added into the uniform solution obtained in the step 2), the balance is supplemented with water, the balance water is controlled to be 5 wt% of the solid content, the mixture is magnetically stirred for 5min, and the mixture is uniformly mixed. Wherein the content of the added initiator is 0.035 wt% of the acrylic acid; the content of the reducing agent added was 0.03% by weight based on the acrylic acid.
4) Pouring the solution obtained in the step 3) into a mould, transferring the mould into an environment with the temperature of-20 ℃, initiating polymerization for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling ratio of the low-temperature super-macroporous sponge is 2085%, the time for reaching swelling equilibrium is less than 5s, the porosity is as high as 95.9%, the low-temperature super-macroporous sponge can be repeatedly used, and the complete shape can be still kept after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and the water absorption rate test shows that the low-temperature super-macroporous sponge can be quickly swelled and balanced (<5 s); after the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 9
1) 5ml of 2 wt% chitosan acetic acid aqueous solution is prepared, 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step 1), and 0.215g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. The acrylic acid content was 10 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 43 wt% of acrylic acid.
3) And (3) adding 0.0525g of initiator ammonium persulfate and 0.0475g of reducing agent potassium metabisulfite into the uniform solution obtained in the step (2), supplementing water to the balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein, the content of the added initiator is 10.5 wt% of the acrylic acid; the content of the reducing agent added was 9.5% by weight of acrylic acid.
4) And (4) pouring the solution obtained in the step (3) into a mould, transferring the mould into an environment with the temperature of-20 ℃, initiating polymerization for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling ratio of the low-temperature super-macroporous sponge is 2240%, the time for reaching swelling balance is less than 5s, the porosity is as high as 95.0%, the sponge can be repeatedly used, and the shape can still be kept intact after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and the water absorption rate test shows that the low-temperature super-macroporous sponge can be quickly swelled and balanced (<5 s); after the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 10
1) 5ml of 2 wt% chitosan acetic acid aqueous solution is prepared, 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step (1), and 0.215g of N, N' -methylenebisacrylamide as a crosslinking agent was added in proportion to obtain a homogeneous solution. The acrylic acid content was 10 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 43 wt% of acrylic acid.
3) And (3) adding 0.025g of initiator ammonium persulfate and 0.0225g of reducing agent potassium metabisulfite into the uniform solution obtained in the step (2), supplementing water to the balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein, the content of the added initiator is 5 wt% of the acrylic acid; the content of the reducing agent added was 4.5% by weight of acrylic acid.
4) Pouring the solution obtained in the step 3) into a mould, transferring the mould into an environment at 0 ℃, initiating polymerization for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling ratio of the super-macroporous low-temperature sponge is 1987%, the swelling equilibrium time is less than 5s, the porosity is as high as 97.3%, the super-macroporous low-temperature sponge can be repeatedly used, and the super-macroporous low-temperature sponge can still keep a complete shape after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and the water absorption rate test shows that the low-temperature super-macroporous sponge can be quickly swelled and balanced (<5 s); after the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 11
1) 5ml of 2 wt% chitosan acetic acid aqueous solution is prepared, 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step (1), and 0.215g of N, N' -methylenebisacrylamide as a crosslinking agent was added in proportion to obtain a homogeneous solution. The acrylic acid content was 10 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 43 wt% of acrylic acid.
3) And (3) adding 0.025g of initiator ammonium persulfate and 0.0225g of reducing agent potassium metabisulfite into the uniform solution obtained in the step (2), supplementing water to the balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein, the content of the added initiator is 5 wt% of the acrylic acid; the content of the reducing agent added was 4.5% by weight of acrylic acid.
4) Pouring the solution obtained in the step 3) into a mould, transferring the mould into an environment with the temperature of-40 ℃, initiating polymerization for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling rate of the low-temperature super-macroporous sponge is 2054%, the time for reaching swelling equilibrium is less than 5s, the porosity is as high as 96.3%, the sponge can be repeatedly used, and the shape can still be kept intact after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and the water absorption rate test shows that the low-temperature super-macroporous sponge can be quickly swelled and balanced (<5 s); after the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 12
1) Preparing 5ml of 2 wt% chitosan acetic acid aqueous solution: 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, a 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step 1), and 0.215g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. Wherein, the content of acrylic acid is 10 wt%; the content of the chitosan is 2 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 43 wt% of acrylic acid.
3) Adding 0.030g of initiator potassium persulfate and 0.0225g of reducing agent potassium metabisulfite into the uniform solution obtained in the step 2), supplementing water in balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein the content of the added initiator is 6 wt% of acrylic acid; the content of the reducing agent added was 4.5% by weight of acrylic acid.
4) Pouring the solution obtained in the step 3) into a mold, transferring the mold into an environment with the temperature of-20 ℃, initiating a free radical polymerization reaction for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling rate of the low-temperature super-macroporous sponge is 1931%, the time for reaching swelling equilibrium is less than 5s, the porosity is as high as 95.2%, the sponge can be repeatedly used, and the shape can still be kept intact after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and the water absorption rate test shows that the low-temperature super-macroporous sponge can be quickly swelled and balanced (<5 s); after the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 13
1) Preparing 5ml of 2 wt% chitosan acetic acid aqueous solution: 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, a 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step 1), and 0.215g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. Wherein, the content of acrylic acid is 3 wt%; the content of the chitosan is 0.5 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 10 wt% of acrylic acid.
3) Adding 0.025g of initiator ammonium persulfate and 0.0105g of reducer sodium bisulfite into the uniform solution obtained in the step 2), supplementing water in balance, controlling the balance to be 5 wt% of the solid content, magnetically stirring for 5min, and uniformly mixing. Wherein the content of the added initiator is 0.35 wt% of the acrylic acid; the content of the reducing agent added was 0.3% by weight of acrylic acid.
4) Pouring the solution obtained in the step 3) into a mold, transferring the mold into an environment with the temperature of-20 ℃, initiating a free radical polymerization reaction for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling rate of the low-temperature super-macroporous sponge 1956%, the time for reaching swelling equilibrium is less than 5s, the porosity is as high as 95.2%, the sponge can be repeatedly used, and the complete shape can be still kept after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and the water absorption rate test shows that the low-temperature super-macroporous sponge can be quickly swelled and balanced (<5 s); after the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
Example 14
1) Preparing 5ml of 2 wt% chitosan acetic acid aqueous solution: 0.1g of chitosan is dissolved in 1 v/v% acetic acid aqueous solution, and under the condition of magnetic stirring, a 2 wt% chitosan uniform solution is obtained.
2) 0.5g of acrylic acid was added dropwise to the homogeneous solution of step 1), and 0.215g of N, N' -methylenebisacrylamide, a crosslinking agent, was added in proportion to obtain a homogeneous solution. Wherein, the content of acrylic acid is 15 wt%; the content of the chitosan is 3 wt%; the content of the added crosslinking agent N, N' -methylenebisacrylamide was 50 wt% of acrylic acid.
3) Adding 0.025g of initiator ammonium persulfate and 0.0160g of reducing agent sodium thiosulfate into the uniform solution obtained in the step 2), supplementing water for the rest, magnetically stirring for 5min, and uniformly mixing. Wherein, the content of the added initiator is 6.5 wt% of the acrylic acid; the content of the reducing agent added was 6 wt% of acrylic acid.
4) Pouring the solution obtained in the step 3) into a mold, transferring the mold into an environment with the temperature of-20 ℃, initiating a free radical polymerization reaction for 24 hours to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the super-macroporous sponge.
The swelling rate of the low-temperature super-macroporous sponge is 1931%, the time for reaching swelling equilibrium is less than 5s, the porosity is as high as 95.2%, the sponge can be repeatedly used, and the shape can still be kept intact after 10 times of circulation.
The hydrophilic performance and the mechanical stability of the sponge are tested, and the water absorption rate test shows that the low-temperature super-macroporous sponge can be quickly swelled and balanced (<5 s); after the strain is 80% through a uniaxial compression test, the low-temperature super-macroporous sponge can still keep a complete shape; still have good structural integrity after 100 compression cycles.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The polyacrylic acid/chitosan super-macroporous low-temperature sponge is characterized by comprising the following raw material components in percentage: 1-20 wt% of acrylic acid; 0.5-5 wt% of chitosan; the content of the cross-linking agent is 1.1 to 86 weight percent of the acrylic acid, and the content of the initiator is 0.035 to 10.5 weight percent of the acrylic acid; the content of the reducing agent is 0.03-9.5 wt% of the acrylic acid; and the balance water.
2. The polyacrylic acid/chitosan ultra-large pore low-temperature sponge according to claim 1, which comprises the following raw material components in percentage by weight: 3-15 wt% of acrylic acid; 0.5-3 wt% of chitosan; the content of the cross-linking agent is 10-50 wt% of acrylic acid; the content of the initiator is 0.35 to 6.5 weight percent of the acrylic acid; the content of the reducing agent is 0.3-6 wt% of the acrylic acid; and the balance water.
Preferably, the feed comprises the following raw material components in percentage by weight: 5-10 wt% of acrylic acid; 1.0-2.0 wt% of chitosan; the content of the cross-linking agent is 20-45 wt% of the acrylic acid; the content of the initiator is 1.05-5 wt% of the acrylic acid; the content of the reducing agent is 0.95-5 wt% of the acrylic acid; and the balance water.
3. The polyacrylic acid/chitosan ultra-large pore low temperature sponge according to claim 1 or 2, wherein the cross-linking agent is N, N' -methylenebisacrylamide; the initiator is selected from ammonium persulfate and/or potassium persulfate; the reducing agent is selected from one or more of potassium metabisulfite, sodium bisulfite and sodium thiosulfate.
4. The method for preparing the polyacrylic acid/chitosan ultra-large pore low temperature sponge as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
1) preparing a chitosan acetic acid aqueous solution, dissolving chitosan in the acetic acid aqueous solution, and obtaining a chitosan acetic acid uniform solution under the condition of magnetic stirring.
2) Dropwise adding an acrylic acid monomer into the chitosan acetic acid homogeneous solution prepared in the step 1), and proportionally adding a cross-linking agent N, N' -methylene bisacrylamide to obtain a homogeneous solution.
3) Adding an initiator and a reducing agent into the uniform solution obtained in the step 2) in proportion, supplementing water to the balance, magnetically stirring, uniformly mixing, transferring the solution into a low-temperature environment below 0 ℃, initiating a free radical polymerization reaction to form a polyacrylic acid/chitosan semi-interpenetrating network, and freeze-drying the obtained low-temperature gel to obtain the polyacrylic acid/chitosan ultra-macroporous low-temperature sponge.
5. The method according to claim 4, wherein the crosslinking agent is N, N' -methylenebisacrylamide; the initiator is selected from one or more of ammonium persulfate and/or potassium persulfate; preferably ammonium persulfate; the reducing agent is selected from one or more of potassium metabisulfite, sodium bisulfite and sodium thiosulfate; potassium metabisulfite is preferred.
6. The production method according to claim 4, wherein the content of the acrylic acid in the homogeneous solution obtained in the step 2) is 1 to 20 wt%; the content of the chitosan is 0.5-5 wt%; the content of the added crosslinking agent N, N' -methylene-bisacrylamide is 1.1-86 wt% of the acrylic acid.
Preferably, the acrylic acid content is 5-10 wt%; the content of the chitosan is 1-5 wt%; the content of the added cross-linking agent N, N' -methylene-bisacrylamide is 20-45 wt% of the acrylic acid.
7. The method according to claim 4, wherein the amount of the initiator added in step 3) is 0.035 to 10.5% by weight based on the acrylic acid; the content of the added reducing agent is 0.03-9.5 wt% of the acrylic acid.
Preferably, the content of the initiator added in the step 3) is 0.35 to 6.5 wt% of acrylic acid; the reducing agent is 0.3-6 wt% of acrylic acid.
More preferably, the content of the initiator added in the step 3) is 1.05 to 5 wt% of acrylic acid; the content of the reducing agent added is 0.95 to 5 wt% of the acrylic acid.
Preferably, the balance of water is controlled to be 3 wt% to 15 wt% of the solid content.
8. The method according to claim 7, wherein the concentration of the aqueous acetic acid solution is 0.5 to 1.5 v/v%; preferably 1 v/v%; the concentration of the chitosan acetic acid homogeneous aqueous solution prepared in the step 1) is 0.5-3.5 wt%; preferably 1.5 wt% to 2.5 wt%; for example, it may be 1.5 wt%, 1.6 wt%, 1.8 wt%, 2.0 wt%, 2.2 wt%, or 2.5 wt%.
9. The preparation method of claim 4, wherein the magnetic stirring is performed for 1-20 minutes in the step 3), the solution is poured into a mold after being uniformly mixed, and the mold is moved into an environment with the temperature of-40 ℃ to 0 ℃ for polymerization for 6-72 hours.
10. Use of the polyacrylic acid/chitosan super macroporous cryogenic sponge of any one of claims 1 to 3 for arterial hemostasis, body surface hemostasis.
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