CN112662001A - Preparation method of biomass material film with intertransmission network structure constructed based on zirconium tanning agent - Google Patents
Preparation method of biomass material film with intertransmission network structure constructed based on zirconium tanning agent Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000002028 Biomass Substances 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 86
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 86
- 239000000661 sodium alginate Substances 0.000 claims abstract description 86
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 85
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 80
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 36
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- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims abstract description 22
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Abstract
The invention discloses a preparation method of a biomass material film based on a zirconium tanning agent construction mutual transmission network structure, which is implemented according to the following steps: step 1, preparing a sodium alginate aqueous solution, and adding a mixed solution prepared by taking isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutaric acid ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane, namely, a first network is constructed; and 2, soaking the isopropyl acrylamide/sodium alginate membrane in a zirconium sulfate solution to finally obtain the high-strength interpenetrating network hydrogel membrane. A preparation method of a biomass material film with an interpenetrating network structure based on a zirconium tanning agent can obtain a high-strength interpenetrating network hydrogel film.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and high-strength hydrogel materials, and particularly relates to a preparation method of a biomass material film with an inter-transmission network structure constructed on the basis of a zirconium tanning agent.
Background
Hydrogel (Hydrogel) is a gel using water as a dispersion medium, and is a high molecular polymer composed of 3D cross-linked networks and water molecules filled between the networks. The hydrogel network contains a large number of hydrophilic groups and partial hydrophobic groups, wherein the hydrophilic residues are combined with water molecules to connect the water molecules in the network, and the hydrophobic residues swell when meeting water, so that the hydrogel shows the characteristics of softness and wetness. The hydrogel has a structure similar to that of biological tissues, and has good hydrophilicity and biocompatibility, so that the hydrogel can be widely applied to the fields of pollution control, agricultural drought resistance, tissue engineering, cartilage repair, drug carriers, intelligent sensors, supercapacitors and the like. However, most hydrogels are generally mechanically weak, which greatly limits the application of hydrogels
In recent years, the research on tough hydrogels has been greatly advanced, and several representative hydrogels with high mechanical properties, such as macromolecular microsphere composite hydrogel, slip ring hydrogel, nanocomposite hydrogel and interpenetrating network hydrogel, have appeared.
An Interpenetrating Polymer Networks (IPN) is abbreviated. Is a network-shaped polymer mixture consisting of two or more crosslinked polymer networks, which was proposed by Millar in 1960, and since the 70 s of the 20 th century, the research on interpenetrating network structure has been increasingly emphasized as a new field of polymer modification. In recent years, interpenetrating network structures have been developed rapidly, both theoretically and practically. In general, IPNs swell in solvents, are insoluble, and are incapable of flow and creep. Most IPNs belong to the two-phase system, rubber phase and plastic phase. In actual production and experiments, the raw materials, crosslinking agents, and reaction conditions may be selected as needed to synthesize a desired polymer compound. Because the space of free play is very large, the interpenetrating network has wide development prospect.
The preparation of interpenetrating networks can be roughly divided into two types, the first type is that the first network is prepared and added into a system containing a cross-linking agent, an initiator and a reaction monomer to swell, and under a certain condition, the monomer reacts to generate a second network, so that the interpenetrating networks are formed. The other is that two or more than two reaction monomers are placed in a reaction container, and the two systems are polymerized and crosslinked respectively to form an interpenetrating network structure. The biggest characteristic is that different macromolecules are tangled together and can not be released. The properties of interpenetrating networks are related to the structure and the method of its preparation, and interpenetrating structures of networks composed of different polymers also differ in their mechanical strength. This is because good two-phase interfacial bonding in interpenetrating networks facilitates transfer and dispersion forces, and reduces the likelihood of two-phase interfacial defects and damage. Therefore, the modulus and the mechanical strength of the material are often higher than the corresponding performance indexes of the grouped polymers, and the synergistic effect is shown.
Disclosure of Invention
The invention aims to provide a preparation method of a biomass material film with an interpenetrating network structure based on a zirconium tanning agent, which can obtain an interpenetrating network hydrogel film with high strength.
The technical scheme adopted by the invention is that the preparation method of the biomass material film with the mutual transmission network structure constructed on the basis of the zirconium tanning agent is implemented according to the following steps:
step 1, preparing a sodium alginate aqueous solution, and adding a mixed solution prepared by taking isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutaric acid ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane, namely, a first network is constructed;
and 2, soaking the isopropyl acrylamide/sodium alginate membrane in a zirconium sulfate solution to finally obtain the high-strength interpenetrating network hydrogel membrane.
The present invention is also characterized in that,
the step 1 is implemented according to the following steps:
step 1.1, preparing a sodium alginate aqueous solution with the concentration of 23-50 mg/ml, fully stirring for 10-20 minutes by using a magnetic stirrer, and standing for 10-20 minutes for later use after the sodium alginate aqueous solution is completely dissolved;
step 1.2, preparing an isopropyl acrylamide aqueous solution with the concentration of 30-100 mg/ml, sequentially adding N, N '-methylene bisacrylamide and alpha-pentanedionic acid, fully stirring for 10-20 minutes by using a magnetic stirrer, and standing for 10-20 minutes after the N, N' -methylene bisacrylamide and the alpha-pentanedionic acid are completely dissolved to obtain a mixed solution for later use;
step 1.3, pouring the mixed solution prepared in the step 1.2 into the sodium alginate aqueous solution obtained in the step 1.1, fully stirring for 5-10 minutes by using a magnetic stirrer, taking out a small beaker, and standing for 10-20 minutes to remove bubbles in the solution to obtain a viscous solution;
step 1.4, uniformly pouring the viscous solution prepared in the step 1.3 into a polytetrafluoroethylene plate, ensuring that the polytetrafluoroethylene plate is uniformly paved with the solution, then putting the polytetrafluoroethylene plate filled with the viscous solution into an ultraviolet crosslinking instrument, irradiating for 3-12 hours under ultraviolet light with the wavelength of 365nm, taking out the prepared isopropyl acrylamide/sodium alginate membrane, and putting the isopropyl acrylamide/sodium alginate membrane into a self-sealing bag for later use.
In the step 1.2, the mass of the added N, N' -methylene-bisacrylamide accounts for 2.0-12% of the mass of the isopropyl acrylamide, and the mass of the added alpha-pentanedionic acid accounts for 0.2-0.6% of the mass of the isopropyl acrylamide.
The specific implementation process of the step 2 is as follows:
and (3) soaking the isopropyl acrylamide/sodium alginate membrane prepared in the step (1.4) in a zirconium sulfate solution of 0.1-0.5 mol/L for 3 hours to obtain the high-strength interpenetrating network hydrogel membrane.
In step 1.4, the use parameters of the ultraviolet crosslinking instrument are as follows: 50W, 365nm, exposure chamber size 34cm × 26cm × l5cm, irradiation distance 15 cm.
The invention has the beneficial effects that: the method of the invention uses metal zirconium ion (Zr) for the first time4+) Forming a second network through coordination crosslinking to obtain the high-strength interpenetrating network hydrogel film.
Drawings
FIG. 1 is an infrared spectrum before and after the zirconium ions are soaked in the isopropyl acrylamide/sodium alginate membrane prepared in step 1.4 of the method of the present invention;
FIG. 2 is a plan SEM photograph of the isopropyl acrylamide/sodium alginate membrane prepared in step 1.4 of the method of the present invention without soaking in a metal ion solution;
FIG. 3 is a plan SEM photograph of the isopropylacrylamide/sodium alginate membrane prepared in step 1.4 of the method of the present invention after soaking in a zirconium ion solution;
FIG. 4 is a longitudinal SEM image of the isopropyl acrylamide/sodium alginate membrane prepared in step 1.4 of the method of the present invention without soaking in a metal ion solution;
FIG. 5 is a longitudinal SEM image of the membrane prepared in step 1.4 of the method of the present invention after soaking in zirconium ion solution;
fig. 6 is a stress-strain diagram of the isopropyl acrylamide/sodium alginate membrane prepared in step 1.4 of the method of the present invention after soaking in a zirconium ion solution.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a biomass material film based on a zirconium tanning agent construction mutual transmission network structure, which is implemented according to the following steps:
step 1, preparing a sodium alginate aqueous solution, and adding a mixed solution prepared by taking isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutaric acid ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane, namely, a first network is constructed;
the step 1 is implemented according to the following steps:
step 1.1, preparing a sodium alginate aqueous solution with the concentration of 23-50 mg/ml, fully stirring for 10-20 minutes by using a magnetic stirrer, and standing for 10-20 minutes for later use after the sodium alginate aqueous solution is completely dissolved;
step 1.2, preparing an isopropyl acrylamide aqueous solution with the concentration of 30-100 mg/ml, sequentially adding N, N '-methylene bisacrylamide and alpha-pentanedionic acid, fully stirring for 10-20 minutes by using a magnetic stirrer, and standing for 10-20 minutes after the N, N' -methylene bisacrylamide and the alpha-pentanedionic acid are completely dissolved to obtain a mixed solution for later use;
in the step 1.2, the mass of the added N, N' -methylene-bisacrylamide accounts for 2.0-12% of the mass of the isopropyl acrylamide, and the mass of the added alpha-pentanedionic acid accounts for 0.2-0.6% of the mass of the isopropyl acrylamide.
Step 1.3, pouring the mixed solution prepared in the step 1.2 into the sodium alginate aqueous solution obtained in the step 1.1, fully stirring for 5-10 minutes by using a magnetic stirrer, taking out a small beaker, and standing for 10-20 minutes to remove bubbles in the solution to obtain a viscous solution;
step 1.4, uniformly pouring the viscous solution prepared in the step 1.3 into a polytetrafluoroethylene plate, ensuring that the polytetrafluoroethylene plate is uniformly paved with the solution, then putting the polytetrafluoroethylene plate filled with the viscous solution into an ultraviolet crosslinking instrument, irradiating for 3-12 hours under ultraviolet light with the wavelength of 365nm, taking out the prepared isopropyl acrylamide/sodium alginate membrane, and putting the isopropyl acrylamide/sodium alginate membrane into a self-sealing bag for later use;
in step 1.4, the use parameters of the ultraviolet crosslinking instrument are as follows: 50W, 365nm, exposure chamber size 34cm × 26cm × l5cm, irradiation distance 15 cm.
And 2, soaking the isopropyl acrylamide/sodium alginate membrane in a zirconium sulfate solution, and performing coordination crosslinking on carboxylate radicals of the sodium alginate and metal cations to form a second network, thereby finally obtaining the high-strength interpenetrating network hydrogel membrane.
The specific implementation process of the step 2 is as follows:
and (3) soaking the isopropyl acrylamide/sodium alginate membrane prepared in the step (1.4) in a zirconium sulfate solution of 0.1-0.5 mol/L for 3 hours to obtain the high-strength interpenetrating network hydrogel membrane. The coordination of the metal zirconium ions and the sodium alginate in the isopropyl sodium alginate film forms a second network structure, and finally an interpenetrating network structure is formed.
The invention is described below in principle:
step 1, constructing a first network by using isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutarate ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane;
isopropyl acrylamide forms a planar net structure under the action of N, N' -methylene bisacrylamide. The long-chain macromolecules are generated by the polyaddition of isopropyl acrylamide under the condition of ultraviolet light, and the unsaturated double bonds at two ends of N, N' -methylene bisacrylamide can form a crosslinking effect between isopropyl acrylamide molecular chains to form a first network. The sodium alginate molecules are embedded in meshes formed by isopropyl acrylamide because of not participating in reaction.
And 2, soaking the isopropyl acrylamide/sodium alginate membrane in a zirconium sulfate solution, and performing coordination crosslinking on carboxylate radicals and metal cations of the sodium alginate to form a second network. Finally obtaining the interpenetrating network hydrogel film.
And soaking the first network and sodium alginate in metal ion solutions with different concentrations, and performing coordination crosslinking on carboxylate radicals and metal cations of the sodium alginate to form a second network. Finally obtaining the high-strength interpenetrating network hydrogel film.
Example 1
A preparation method of a biomass material film based on a zirconium tanning agent construction mutual transmission network structure is implemented according to the following steps:
step 1, preparing a sodium alginate aqueous solution, and adding a mixed solution prepared by taking isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutaric acid ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane, namely, a first network is constructed;
the step 1 is implemented according to the following steps:
step 1.1, preparing a sodium alginate aqueous solution with the concentration of 50.0mg/ml, fully stirring for 10 minutes by using a magnetic stirrer, and standing for 10 minutes for later use after the sodium alginate aqueous solution is completely dissolved;
step 1.2, preparing an isopropyl acrylamide aqueous solution with the concentration of 100.0mg/ml, sequentially adding N, N '-methylene bisacrylamide and alpha-pentanedionic acid, fully stirring for 10 minutes by using a magnetic stirrer, and standing for 10 minutes after the N, N' -methylene bisacrylamide and the alpha-pentanedionic acid are completely dissolved to obtain a mixed solution for later use;
in step 1.2, the mass of N, N' -methylenebisacrylamide added was 3.9% of the mass of isopropylacrylamide, and the mass of α -pentanedionic acid added was 0.2% of the mass of isopropylacrylamide.
Step 1.3, pouring the mixed solution prepared in the step 1.2 into the sodium alginate aqueous solution obtained in the step 1.1, fully stirring for 5 minutes by using a magnetic stirrer, taking out a small beaker, and standing for 10 minutes to remove bubbles in the solution to obtain a viscous solution;
step 1.4, uniformly pouring the viscous solution prepared in the step 1.3 into a polytetrafluoroethylene plate, ensuring that the polytetrafluoroethylene plate is uniformly paved with the solution, then putting the polytetrafluoroethylene plate filled with the viscous solution into an ultraviolet crosslinking instrument, irradiating for 3 hours under ultraviolet light with the wavelength of 365nm, taking out the prepared isopropyl acrylamide/sodium alginate membrane, and putting the membrane into a self-sealing bag for later use;
in step 1.4, the use parameters of the ultraviolet crosslinking instrument are as follows: 50W, 365nm, exposure chamber size 34cm × 26cm × l5cm, irradiation distance 15 cm.
And 2, soaking the isopropyl acrylamide/sodium alginate membrane prepared in the step 1.4 in 0.3mol/L zirconium sulfate solution for 3 hours to obtain the high-strength interpenetrating network hydrogel membrane.
The specific preparation steps of the 0.3mol/L zirconium sulfate solution in the step 2 are as follows:
the specific preparation steps of the solution containing 0.3mol/L zirconium ions are as follows:
weighing 8.5g of zirconium sulfate, dissolving with 50mL of distilled water, then fixing the volume with a 100mL volumetric flask, preparing 0.3mol/L zirconium sulfate solution, and standing for later use.
As shown in FIG. 1, in the case of non-Zr-impregnated alloy4+Front, at 3290cm-1A sharp peak due to the stretching vibration of N-H, 1620cm-1Symmetric stretching vibration with peak at 709cm-1The peak shows that O-H in the sodium alginate molecule is out-of-plane bending and vibrating. Soaking in Zr4+After that, at 3290cm-1There is a clear peak intensity reduction due to the association of H on N-H. And at 1620cm-1There is also a different degree of reduction in the intensity of the peaks. This proves Zr4+And the complex reaction is carried out with the carboxylate radical on the sodium alginate. At 709cm-1The peak appeared to disappear due to the hydroxyl groups on the sodium alginate molecule and Zr4+Take place ofAnd (4) carrying out coordination reaction.
Soaking Zr as shown in FIGS. 2 and 34+The isopropyl acrylamide/sodium alginate membrane has larger pores, a rougher surface and a two-dimensional network structure; soaking Zr4+After that, the pores of the film were reduced and the surface was relatively smooth, proving that Zr4+And the complex reacts with carboxylate radical on sodium alginate to form a second network, and finally a three-dimensional structure is formed.
As shown in fig. 4 and 5, it can be seen from fig. 4 that the longitudinal section of the isopropyl acrylamide/sodium alginate membrane is layered and superposed, because a first network structure is formed during the polymerization of isopropyl acrylamide, and when metal ions penetrate into the meshes and react with sodium alginate, a second network structure is formed. Finally, an interpenetrating network structure is formed, and as can be seen from fig. 5, holes appear on the longitudinal section after the metal ions are soaked.
As shown in fig. 6, when the strain initially increases after soaking in zirconium ions, the corresponding stress rise amplitude is small, and as the stress increases, the film breaks when the strain reaches 8.9%, and the breaking strength is 29.25MPa, which indicates that the flexibility of the film is improved and the breaking strength is improved.
Example 2
A preparation method of a biomass material film based on a zirconium tanning agent construction mutual transmission network structure is implemented according to the following steps:
step 1, preparing a sodium alginate aqueous solution, and adding a mixed solution prepared by taking isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutaric acid ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane, namely, a first network is constructed;
the step 1 is implemented according to the following steps:
step 1.1, preparing a sodium alginate aqueous solution with the concentration of 33.3mg/ml, fully stirring for 10 minutes by using a magnetic stirrer, and standing for 10 minutes for later use after the sodium alginate aqueous solution is completely dissolved;
step 1.2, preparing an isopropyl acrylamide aqueous solution with the concentration of 100.0mg/ml, sequentially adding N, N '-methylene bisacrylamide and alpha-pentanedionic acid, fully stirring for 10 minutes by using a magnetic stirrer, and standing for 10 minutes after the N, N' -methylene bisacrylamide and the alpha-pentanedionic acid are completely dissolved to obtain a mixed solution for later use;
in step 1.2, the mass of N, N' -methylenebisacrylamide added was 3.9% of the mass of isopropylacrylamide, and the mass of α -pentanedionic acid added was 0.2% of the mass of isopropylacrylamide.
Step 1.3, pouring the mixed solution prepared in the step 1.2 into the sodium alginate aqueous solution obtained in the step 1.1, fully stirring for 5 minutes by using a magnetic stirrer, taking out a small beaker, and standing for 10 minutes to remove bubbles in the solution to obtain a viscous solution;
step 1.4, uniformly pouring the viscous solution prepared in the step 1.3 into a polytetrafluoroethylene plate, ensuring that the polytetrafluoroethylene plate is uniformly paved with the solution, then putting the polytetrafluoroethylene plate filled with the viscous solution into an ultraviolet crosslinking instrument, irradiating for 3 hours under ultraviolet light with the wavelength of 365nm, taking out the prepared isopropyl acrylamide/sodium alginate membrane, and putting the membrane into a self-sealing bag for later use;
in step 1.4, the use parameters of the ultraviolet crosslinking instrument are as follows: 50W, 365nm, exposure chamber size 34cm × 26cm × l5cm, irradiation distance 15 cm.
And 2, soaking the isopropyl acrylamide/sodium alginate membrane prepared in the step 1.4 in 0.1mol/L zirconium sulfate solution for 3 hours to obtain the high-strength interpenetrating network hydrogel membrane.
The specific preparation steps of the 0.3mol/L zirconium sulfate solution in the step 2 are as follows:
the specific preparation steps of the solution containing 0.1mol/L zirconium ions are as follows:
2.833g of zirconium sulfate is weighed, dissolved in 50mL of distilled water, and then the volume is determined by using a 100mL volumetric flask, so as to prepare a 0.1mol/L zirconium sulfate solution, and the solution is placed for standby.
Example 3
A preparation method of a biomass material film based on a zirconium tanning agent construction mutual transmission network structure is implemented according to the following steps:
step 1, preparing a sodium alginate aqueous solution, and adding a mixed solution prepared by taking isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutaric acid ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane, namely, a first network is constructed;
the step 1 is implemented according to the following steps:
step 1.1, preparing a sodium alginate aqueous solution with the concentration of 33.3mg/ml, fully stirring for 20 minutes by using a magnetic stirrer, and standing for 20 minutes for later use after the sodium alginate aqueous solution is completely dissolved;
step 1.2, preparing an isopropyl acrylamide aqueous solution with the concentration of 66.6mg/ml, sequentially adding N, N '-methylene bisacrylamide and alpha-pentanedionic acid, fully stirring for 20 minutes by using a magnetic stirrer, and standing for 20 minutes after the N, N' -methylene bisacrylamide and the alpha-pentanedionic acid are completely dissolved to obtain a mixed solution for later use;
in step 1.2, the mass of N, N' -methylenebisacrylamide added was 5.8% of the mass of isopropylacrylamide, and the mass of α -pentanedionic acid added was 0.3% of the mass of isopropylacrylamide.
Step 1.3, pouring the mixed solution prepared in the step 1.2 into the sodium alginate aqueous solution obtained in the step 1.1, fully stirring for 5-10 minutes by using a magnetic stirrer, taking out a small beaker, and standing for 10-20 minutes to remove bubbles in the solution to obtain a viscous solution;
step 1.4, uniformly pouring the viscous solution prepared in the step 1.3 into a polytetrafluoroethylene plate, ensuring that the polytetrafluoroethylene plate is uniformly paved with the solution, then putting the polytetrafluoroethylene plate filled with the viscous solution into an ultraviolet crosslinking instrument, irradiating for 12 hours under ultraviolet light with the wavelength of 365nm, taking out the prepared isopropyl acrylamide/sodium alginate membrane, and putting the membrane into a self-sealing bag for later use;
in step 1.4, the use parameters of the ultraviolet crosslinking instrument are as follows: 50W, 365nm, exposure chamber size 34cm × 26cm × l5cm, irradiation distance 15 cm.
And 2, soaking the isopropyl acrylamide/sodium alginate membrane prepared in the step 1.4 in 0.1-0.5 mol/L zirconium sulfate solution for 3 hours to obtain the high-strength interpenetrating network hydrogel membrane.
The specific preparation steps of the 0.5mol/L zirconium sulfate solution in the step 2 are as follows:
the specific preparation steps of the solution containing 0.5mol/L zirconium ions are as follows:
14.167g of zirconium sulfate is weighed, dissolved in 50mL of distilled water, and then the volume is determined by a 100mL volumetric flask, and a 0.3mol/L zirconium sulfate solution is prepared and placed for standby.
Example 4
A preparation method of a biomass material film based on a zirconium tanning agent construction mutual transmission network structure is implemented according to the following steps:
step 1, preparing a sodium alginate aqueous solution, and adding a mixed solution prepared by taking isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutaric acid ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane, namely, a first network is constructed;
the step 1 is implemented according to the following steps:
step 1.1, preparing a sodium alginate aqueous solution with the concentration of 33.3mg/ml, fully stirring for 15 minutes by using a magnetic stirrer, and standing for 15 minutes for later use after the sodium alginate aqueous solution is completely dissolved;
step 1.2, preparing an isopropyl acrylamide aqueous solution with the concentration of 50mg/ml, sequentially adding N, N '-methylene bisacrylamide and alpha-pentanedionic acid, fully stirring for 15 minutes by using a magnetic stirrer, and standing for 15 minutes after the N, N' -methylene bisacrylamide and the alpha-pentanedionic acid are completely dissolved to obtain a mixed solution for later use;
in step 1.2, the mass of N, N' -methylenebisacrylamide added was 7.7% of the mass of isopropylacrylamide, and the mass of α -pentanedionic acid added was 0.4% of the mass of isopropylacrylamide.
Step 1.3, pouring the mixed solution prepared in the step 1.2 into the sodium alginate aqueous solution obtained in the step 1.1, fully stirring for 7 minutes by using a magnetic stirrer, taking out a small beaker, and standing for 15 minutes to remove bubbles in the solution to obtain a viscous solution;
step 1.4, uniformly pouring the viscous solution prepared in the step 1.3 into a polytetrafluoroethylene plate, ensuring that the polytetrafluoroethylene plate is uniformly paved with the solution, then putting the polytetrafluoroethylene plate filled with the viscous solution into an ultraviolet crosslinking instrument, irradiating for 8 hours under ultraviolet light with the wavelength of 365nm, taking out the prepared isopropyl acrylamide/sodium alginate membrane, and putting the membrane into a self-sealing bag for later use;
in step 1.4, the use parameters of the ultraviolet crosslinking instrument are as follows: 50W, 365nm, exposure chamber size 34cm × 26cm × l5cm, irradiation distance 15 cm.
And 2, soaking the isopropyl acrylamide/sodium alginate membrane prepared in the step 1.4 in 0.3mol/L zirconium sulfate solution for 3 hours to obtain the high-strength interpenetrating network hydrogel membrane.
Example 5
A preparation method of a biomass material film based on a zirconium tanning agent construction mutual transmission network structure is implemented according to the following steps:
step 1, preparing a sodium alginate aqueous solution, and adding a mixed solution prepared by taking isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutaric acid ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane, namely, a first network is constructed;
the step 1 is implemented according to the following steps:
step 1.1, preparing a sodium alginate aqueous solution with the concentration of 33.3mg/ml, fully stirring for 19 minutes by using a magnetic stirrer, and standing for 19 minutes for later use after the sodium alginate aqueous solution is completely dissolved;
step 1.2, preparing an isopropyl acrylamide aqueous solution with the concentration of 50mg/ml, sequentially adding N, N '-methylene bisacrylamide and alpha-pentanedionic acid, fully stirring for 10-20 minutes by using a magnetic stirrer, and standing for 15 minutes after the N, N' -methylene bisacrylamide and the alpha-pentanedionic acid are completely dissolved to obtain a mixed solution for later use;
in step 1.2, the mass of N, N' -methylenebisacrylamide added was 5.1% of the mass of isopropylacrylamide, and the mass of α -pentanedionic acid added was 0.4% of the mass of isopropylacrylamide.
Step 1.3, pouring the mixed solution prepared in the step 1.2 into the sodium alginate aqueous solution obtained in the step 1.1, fully stirring for 5 minutes by using a magnetic stirrer, taking out a small beaker, and standing for 20 minutes to remove bubbles in the solution to obtain a viscous solution;
step 1.4, uniformly pouring the viscous solution prepared in the step 1.3 into a polytetrafluoroethylene plate, ensuring that the polytetrafluoroethylene plate is uniformly paved with the solution, then putting the polytetrafluoroethylene plate filled with the viscous solution into an ultraviolet crosslinking instrument, irradiating for 3 hours under ultraviolet light with the wavelength of 365nm, taking out the prepared isopropyl acrylamide/sodium alginate membrane, and putting the membrane into a self-sealing bag for later use;
in step 1.4, the use parameters of the ultraviolet crosslinking instrument are as follows: 50W, 365nm, exposure chamber size 34cm × 26cm × l5cm, irradiation distance 15 cm.
And 2, soaking the isopropyl acrylamide/sodium alginate membrane prepared in the step 1.4 in 0.5mol/L zirconium sulfate solution for 3 hours to obtain the high-strength interpenetrating network hydrogel membrane.
Claims (5)
1. The preparation method of the biomass material film based on the zirconium tanning agent construction mutual transmission network structure is characterized by comprising the following steps:
step 1, preparing a sodium alginate aqueous solution, and adding a mixed solution prepared by taking isopropyl acrylamide as a monomer, N, N' -methylene bisacrylamide as a cross-linking agent and alpha-glutaric acid ketone as an initiator to prepare an isopropyl acrylamide/sodium alginate membrane, namely, a first network is constructed;
and 2, soaking the isopropyl acrylamide/sodium alginate membrane in a zirconium sulfate solution to finally obtain the high-strength interpenetrating network hydrogel membrane.
2. The preparation method of the biomass material film based on the zirconium tanning agent construction mutual transmission network structure according to claim 1, characterized in that the step 1 is specifically implemented according to the following steps:
step 1.1, preparing a sodium alginate aqueous solution with the concentration of 23-50 mg/ml, fully stirring for 10-20 minutes by using a magnetic stirrer, and standing for 10-20 minutes for later use after the sodium alginate aqueous solution is completely dissolved;
step 1.2, preparing an isopropyl acrylamide aqueous solution with the concentration of 30-100 mg/ml, sequentially adding N, N '-methylene bisacrylamide and alpha-pentanedionic acid, fully stirring for 10-20 minutes by using a magnetic stirrer, and standing for 10-20 minutes after the N, N' -methylene bisacrylamide and the alpha-pentanedionic acid are completely dissolved to obtain a mixed solution for later use;
step 1.3, pouring the mixed solution prepared in the step 1.2 into the sodium alginate aqueous solution obtained in the step 1.1, fully stirring for 5-10 minutes by using a magnetic stirrer, taking out a small beaker, and standing for 10-20 minutes to remove bubbles in the solution to obtain a viscous solution;
step 1.4, uniformly pouring the viscous solution prepared in the step 1.3 into a polytetrafluoroethylene plate, ensuring that the polytetrafluoroethylene plate is uniformly paved with the solution, then putting the polytetrafluoroethylene plate filled with the viscous solution into an ultraviolet crosslinking instrument, irradiating for 3-12 hours under ultraviolet light with the wavelength of 365nm, taking out the prepared isopropyl acrylamide/sodium alginate membrane, and putting the isopropyl acrylamide/sodium alginate membrane into a self-sealing bag for later use.
3. The method for preparing the biomass material film based on the zircon tanning agent construction mutual transmission network structure according to claim 2, wherein in the step 1.2, the mass of the added N, N' -methylene-bis-acrylamide is 2.0-12% of the mass of the isopropyl acrylamide, and the mass of the added alpha-pentanedionic acid is 0.2-0.6% of the mass of the isopropyl acrylamide.
4. The preparation method of the biomass material film based on the zirconium tanning agent construction mutual transmission network structure according to claim 2, characterized in that the specific implementation process of the step 2 is as follows:
and (3) soaking the isopropyl acrylamide/sodium alginate membrane prepared in the step (1.4) in a zirconium sulfate solution of 0.1-0.5 mol/L for 3 hours to obtain the high-strength interpenetrating network hydrogel membrane.
5. The method for preparing the biomass material film based on the zirconium tanning agent for constructing the intercommunicating network structure according to the claim 2, wherein in the step 1.4, the using parameters of the ultraviolet cross-linking instrument are as follows: 50W, 365nm, exposure chamber size 34cm × 26cm × l5cm, irradiation distance 15 cm.
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