CN115746381A - Preparation method of porous hydrogel based on microbubble template - Google Patents

Preparation method of porous hydrogel based on microbubble template Download PDF

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CN115746381A
CN115746381A CN202211587887.XA CN202211587887A CN115746381A CN 115746381 A CN115746381 A CN 115746381A CN 202211587887 A CN202211587887 A CN 202211587887A CN 115746381 A CN115746381 A CN 115746381A
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polymer solution
porous
porous hydrogel
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金少搏
叶国永
韦学勇
杨贵先
张志远
李立伟
曹娜
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Zhengzhou University of Light Industry
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Abstract

A method for preparing porous hydrogel based on a microbubble template uses a microfluidic chip device comprising a glass substrate, wherein a microchannel system with a specific microchannel structure is bonded on the glass substrate; based on the micro-channel structure of the micro-fluidic chip device, the gas is sheared by the high-speed flowing polymer solution to realize the uniform and rapid preparation of bubbles; under the induction of freeze-thaw cycle, the liquid polymer in the liquid-state microbubbles is crosslinked and solidified into the porous material wall, and the gas in the microbubbles is converted into a porous structure; according to the invention, the crosslinking of polyvinyl alcohol microbubble polymer is realized through freeze-thaw cycle to prepare the porous hydrogel material, the liquid polymer in the liquid microbubbles is crosslinked and solidified into the porous material wall, and the gas in the microbubbles is converted into a porous structure, so that the complicated step of removing the template can be avoided, the biocompatibility is good, and the preparation process is pollution-free.

Description

Preparation method of porous hydrogel based on microbubble template
Technical Field
The invention relates to the field of preparation of porous hydrogel, in particular to a preparation method of porous hydrogel based on a microbubble template.
Background
The porous hydrogel material has a porous structure inside and is interwoven into a network structure, and has the advantages of small density, large specific surface area, high porosity, good water vapor permeability, good adsorption performance, certain mechanical properties and good rebound resilience. In the aspect of materials, the hydrogel is a soft polymer material with a hydrophilic three-dimensional network structure, the polymer network can absorb a large amount of water or other liquid to swell, and the porous hydrogel material has super-strong hygroscopicity and degradability, so that the effective utilization of resources can be realized in a more environment-friendly manner; the special soft function of the hydrogel can promote the hydrogel to be in more effective contact with a wound, the hydrogel has the advantage of high water content similar to an extracellular matrix structure after absorbing water, the water content is up to 96%, the moist environment of a wound surface can be maintained, a good moist environment is provided for the wound, and the hydrogel has a good effect of promoting wound healing. Therefore, the porous hydrogel material can rapidly absorb wound exudate, resist bacteria, stop bleeding and accelerate wound healing, is proved in medical and biological repair experiments, and is applied to novel medical dressings at present.
Among the many methods for preparing porous hydrogel materials, freeze-drying, porogen, foaming, templating, and the like are commonly used. Although the porous hydrogel prepared by the freeze-drying method has the advantages of simple operation, low material preparation cost, environmental friendliness and the like, and the influence of other chemicals introduced to the biocompatibility of the scaffold material can be avoided by removing water crystals, the porous structure prepared by the method has the defects of irregular shape after drying, difficulty in control, easiness in forming closed pores and the like. The preparation method for preparing the porous material by the pore-forming method is simple and has low cost, but most of the formed pore structures are independent and not communicated with each other, and the pore diameter uniformity is poorer than that of other pore-forming methods; and the removal of the pore-foaming agent needs complex processes of soaking, washing, dissolving and the like, and wastes time and labor. In the process of preparing the porous scaffold by the phase separation method, the sizes and the porosity of pores are difficult to control, and the phenomena of compact surface layer and closed pores sometimes occur.
The template technology is one of the most extensive technologies for preparing the porous hydrogel material at present, and has great advantages in controlling the porosity, the pore size distribution and other structural characteristics of the porous hydrogel material. Currently, porous hydrogel materials are reported to prepare hard templates such as template organic crystals, latex particles, ice and the like, but the biological method using the hard templates requires that after the polymer material is solidified, the templates are removed by high-temperature melting or solvent cleaning to finally form the porous hydrogel materials. In addition, a new method for performing a porous hydrogel material by using microbubbles as a template is reported, but due to the problem that polyvinyl alcohol is easy to collapse in a freeze-thaw cycle, a common method in the prior art is to use polymer solid reagents such as polyvinyl alcohol, gelatin, sodium dodecyl sulfate and the like to be mixed into deionized water in a ratio to obtain a required polymer solution, further prepare low-viscosity liquid microbubbles, and introduce the low-viscosity microbubbles into high-viscosity polymer liquid, but the porous hydrogel material obtained by the method cannot effectively promote wound healing and skin regeneration. In addition, in the prior art, the preparation process is carried out at room temperature, and the micro-fluidic chip device is used for preparing low-viscosity liquid microbubbles by the preliminarily prepared polymer solution through the micro-fluidic chip device at room temperature and then introducing the low-viscosity microbubbles into high-viscosity polymer liquid, so that the preparation steps are complicated.
Disclosure of Invention
In order to solve the defects and improve the preparation capacity of the porous hydrogel material, the invention provides the preparation method of the porous hydrogel based on the microbubble template, microbubbles with controllable sizes are generated by a microfluidic chip device to serve as the template, and the complicated step of removing the template can be avoided; the crosslinking of polyvinyl alcohol microbubble polymer is realized through freeze-thaw cycle to prepare the porous hydrogel material, the biocompatibility is good, and the preparation process is pollution-free; the strength of the porous material is enhanced and the success rate of preparation is improved by the compound use of the gelatin material; by introducing the glucan, the wound healing and the skin regeneration can be promoted; the porosity of the porous hydrogel material can be controlled by the size of the microbubbles.
The object of the invention is achieved in the following way:
a preparation method of a porous hydrogel based on a microbubble template comprises the following steps:
A0. preparing a polymer solution; filling the prepared polymer solution into a polymer solution storage bottle;
A1. placing the microfluidic chip device, the polymer solution and the polymer solution storage bottle in a constant temperature box, preparing liquid micro bubbles by using the microfluidic chip device, and conveying the liquid micro bubbles to a low-temperature environment for collection and storage;
A2. through freeze thawing cycle induction, liquid polymers in the liquid microbubbles are crosslinked and solidified into porous material walls, and gas in the microbubbles is converted into the porous material;
A3. freeze-drying the porous material to remove water in the material, and preparing a hydrophilic primary polyvinyl alcohol pore gel material;
A4. and (3) chemically modifying the primary polyvinyl alcohol pore gel material, changing the original micro-nano structure, and forming a honeycomb structure on the pore wall to prepare the super-hydrophobic porous hydrogel.
Further, the step A0 of configuring the polymer solution process is specifically operated as follows: the preparation method comprises the steps of weighing polymer solid reagents such as polyvinyl alcohol, gelatin, glucan, sodium dodecyl sulfate and the like according to a certain proportion, mixing the polymer solid reagents into deionized water, putting the mixture into a magnetic stirring water pot, heating the mixture to 90 ℃, quickly stirring the mixture for 3 hours by using a magnetic stirrer to quickly dissolve the polyvinyl alcohol, the gelatin, the glucan and the sodium dodecyl sulfate, and then standing the mixture to normal temperature to obtain the required polymer solution.
Furthermore, the molecular weight of the polyvinyl alcohol is 80000-90000, the mass fraction is 15%, the mass fraction of glucan (T-70) is 1%, the mass fraction of gelatin is 5%, and the mass fraction of sodium dodecyl sulfate is 1%, wherein the mass fractions are relative to the mass of deionized water, 100 g of deionized water is taken as ions, and 15 g of polyvinyl alcohol, 1 g of glucan, 5 g of gelatin and 1 g of sodium dodecyl sulfate are added.
Furthermore, the microfluidic chip device comprises a glass substrate, wherein a microchannel system with a specific microchannel structure is bonded on the glass substrate; the micro-channel system comprises a solution flow channel and a gas flow channel, wherein the inlet end of the solution flow channel is a solution inlet, the outlet end of the solution flow channel is communicated with a solution outlet through a snake-shaped flow channel, the inlet end of the gas flow channel is a gas inlet, and the outlet end of the gas flow channel is communicated with the middle part of the solution flow channel; the solution inlet is connected with one end of a first Teflon hose, the other end of the first Teflon hose is connected with a polymer solution storage bottle, the gas inlet is connected with one end of a second Teflon hose, the other end of the second Teflon hose is connected with an air storage bottle, the polymer solution storage bottle and the air storage bottle are both connected with a nitrogen pressure injection pump, the solution outlet is connected with one end of a third Teflon hose, and the other end of the third Teflon hose extends into the glass container; the microchannel system is made of polydimethylsiloxane.
Further, the specific operation of preparing the liquid microbubbles based on the microfluidic chip device in the step A1 is as follows: firstly, placing a microfluidic chip device, a polymer solution and a polymer solution storage bottle in a 60-degree constant temperature box, and placing a glass container in a zero-temperature low-temperature environment; starting a nitrogen pressure injection pump, adjusting proper pressure, and respectively pressing the polymer solution in the polymer solution storage bottle and the gas in the air storage bottle into a solution flow channel and a gas flow channel through a first Teflon hose and a second Teflon hose and enabling the polymer solution and the gas to flow at high speed; the gas in the gas flow passage rapidly generates uniform micro-bubbles under the shearing of the fluid of the polymer solution flowing at high speed in the solution flow passage, and finally flows into the glass container through the third Teflon hose for collection.
Further, the gas is air or nitrogen.
Further, the specific operation procedures induced by freeze-thaw cycling in the step A2 are as follows:
a21: freezing the liquid microbubbles collected in the glass container in a freezing device with freezing temperature of-20 ℃ for 12 hours, taking out the liquid microbubbles and placing the liquid microbubbles in a refrigerator with melting temperature of 4 ℃ for 12 hours;
a22: repeating A21 again;
a23: continuing to freeze the material after A22 at-20 deg.C for 12 hr, storing in a freezing device with 4 deg.C for 1 hr, and storing at room temperature of 25 deg.C for 12 hr;
a24: repeating A23 again to obtain a preliminarily gelled porous hydrogel material.
Further, the specific operation flow of step A3 is as follows: removing water in the porous hydrogel material by using a freeze dryer, pre-freezing the preliminarily gelled porous hydrogel material at the temperature of-20 ℃, and then gradually heating from-20 ℃ to 20 ℃ in a step of 4 ℃ within the temperature range of-20 ℃ to 20 ℃; after 20 hours, a hydrophilic primary polyvinyl alcohol pore gel material was obtained.
Further, the specific operation flow of step A4 is as follows: immersing the primary polyvinyl alcohol pore gel material in a beaker containing 3M Novec 7500 electronic fluorinated oil with the mass fraction of 5 thousandths of 1H, 2H-perfluorooctyltrichlorosilane, heating for 12 hours in a vacuum oven with the set temperature of 50 ℃, and then taking out the primary polyvinyl alcohol pore gel material from the beaker and placing the primary polyvinyl alcohol pore gel material in the vacuum oven to dry for 6 hours at the temperature of 50 ℃ to obtain the super-hydrophobic porous hydrogel.
Compared with the prior art, the invention has the following technical effects:
(1) According to the invention, the crosslinking of the polyvinyl alcohol microbubble polymer is realized through freeze-thaw cycle to prepare the porous hydrogel material, so that the complicated step of template removal can be avoided, the biocompatibility is good, and the preparation process is pollution-free.
(2) When the polymer solution is prepared, wound healing and skin regeneration can be promoted through the introduction of glucan.
(3) In the invention, micro-bubbles with controllable sizes are generated by the micro-fluidic chip device to serve as a template, and the size of the pore structure of the prepared porous material can be regulated and controlled by the size of the micro-bubbles.
(4) According to the invention, the microfluidic chip device, the polymer solution and the polymer liquid storage device are arranged in the thermostat, and the high-viscosity fluid can be used for directly preparing the liquid polymer foam template by heating the microfluidic chip, so that the preparation process is simpler.
Drawings
Fig. 1 is a schematic view of the structure of a microbubble preparation apparatus according to the present invention.
Fig. 2 is a schematic diagram of the microbubble generation process of the present invention.
Fig. 3 is an experimental diagram of the microbubble generation process of the present invention (left) and a microbubble optical image (right).
Fig. 4 is a schematic diagram of the liquid microbubbles cross-linked into the porous material according to the invention.
FIG. 5 is a contact angle image of a drop of porous hydrogel material prepared according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the porous hydrogel based on the microbubble template comprises the following steps:
A0. preparing a polymer solution; filling the prepared polymer solution into a polymer solution storage bottle;
A1. placing the microfluidic chip device, the polymer solution and the polymer solution storage bottle in a constant temperature box, preparing liquid micro bubbles by using the microfluidic chip device, and conveying the liquid micro bubbles to a low-temperature environment for collection and storage;
A2. through freeze thawing cycle induction, liquid polymers in the liquid microbubbles are crosslinked and solidified into porous material walls, and gas in the microbubbles is converted into the porous material;
A3. freeze-drying the porous material to remove water in the material, and preparing a hydrophilic primary polyvinyl alcohol pore gel material;
A4. and chemically modifying the primary polyvinyl alcohol pore gel material, changing the original micro-nano structure, and forming a honeycomb structure on the pore wall to prepare the super-hydrophobic porous hydrogel.
The polymer solution preparation process in the step A0 is specifically operated as follows: the preparation method comprises the steps of weighing polymer solid reagents such as polyvinyl alcohol, gelatin, glucan, sodium dodecyl sulfate and the like according to a certain proportion, mixing the polymer solid reagents into deionized water, putting the mixture into a magnetic stirring water pot, heating the mixture to 90 ℃, quickly stirring the mixture for 3 hours by using a magnetic stirrer to quickly dissolve the polyvinyl alcohol, the gelatin, the glucan and the sodium dodecyl sulfate, and then standing the mixture to normal temperature to obtain the required polymer solution.
The glucan mainly enables the porous hydrogel material to have the functions of promoting wound healing and skin regeneration, the gelatin is used for preventing the porous material from collapsing in the preparation process and enhancing the biocompatibility of the material, and the sodium dodecyl sulfate is used as a surfactant to maintain the stability of polymer microbubbles and avoid fusion among the bubbles.
As shown in fig. 1-2, the microfluidic chip device includes a glass substrate 1, and a microchannel system 2 having a specific microchannel structure is bonded on the glass substrate 1; the micro-channel system 2 comprises a solution channel 5 and a gas channel 8, wherein the inlet end of the solution channel 5 is a solution inlet 3, the outlet end of the solution channel 5 is communicated with a solution outlet 11 through a snake-shaped channel 9, the inlet end of the gas channel 8 is a gas inlet 7, and the outlet end of the gas channel 8 is communicated with the middle part of the solution channel 5; the solution inlet 3 is connected with one end of a first Teflon hose 4, the other end of the first Teflon hose 4 is connected with a polymer solution storage bottle, the gas inlet 7 is connected with one end of a second Teflon hose 6, the other end of the second Teflon hose 6 is connected with an air storage bottle, the polymer solution storage bottle and the air storage bottle are both connected with a nitrogen pressure injection pump, the solution outlet 11 is connected with one end of a third Teflon hose 10, and the other end of the third Teflon hose 10 extends into a glass container 12; the microchannel system 2 is made of polydimethylsiloxane.
The specific operation of preparing the liquid microbubbles based on the microfluidic chip device in the step A1 is as follows: firstly, placing a microfluidic chip device, a polymer solution and a polymer solution storage bottle in a 60-degree constant temperature box to reduce the viscosity of the polymer solution and increase the fluidity; and the glass container 12 is placed in a low temperature environment of zero degrees to prevent the bubble from expanding and cracking; starting a nitrogen pressure injection pump, adjusting proper pressure, and respectively pressing the polymer solution in the polymer solution storage bottle and the gas in the air storage bottle into the solution flow passage 5 and the gas flow passage 8 through the first Teflon hose 4 and the second Teflon hose 6 and flowing at high speed; the gas in the gas flow passage 8 rapidly generates uniform micro-bubbles under the fluid shear of the polymer solution flowing at high speed in the solution flow passage 5, and finally flows into the glass container 12 through the third Teflon hose 10 to be collected; by regulating and controlling different pressures, micro-bubbles with different sizes can be prepared.
The gas is air or nitrogen.
The specific operation flow of the freeze-thaw cycle induction in the step A2 comprises the following steps:
a21: freezing the liquid microbubbles collected in the glass container 12 in a freezing device with a freezing temperature of-20 ℃ for 12 hours, and then taking out and placing in a refrigerator with a melting temperature of 4 ℃ for 12 hours;
a22: repeating A21 again;
a23: continuing to freeze the material after A22 at-20 deg.C for 12 hr, storing in a freezing device with 4 deg.C for 1 hr, and storing at room temperature of 25 deg.C for 12 hr;
a24: repeating A23 again to obtain a preliminarily gelled porous hydrogel material.
The specific operation flow of the step A3 is as follows: removing water in the porous hydrogel material by using a freeze dryer, pre-freezing the preliminarily gelled porous hydrogel material at the temperature of-20 ℃, and then gradually heating from-20 ℃ to 20 ℃ in a step of 4 ℃ within the temperature range of-20 ℃ to 20 ℃; after 20 hours, a hydrophilic primary polyvinyl alcohol pore gel material was obtained.
The specific operation flow of the step A4 is as follows: immersing the primary polyvinyl alcohol pore gel material in a beaker containing 3M Novec 7500 electronic fluorinated oil with the mass fraction of 5 thousandths 1H,2H and 2H-perfluorooctyltrichlorosilane, heating for 12 hours in a vacuum oven with the set temperature of 50 ℃, and then taking out the primary polyvinyl alcohol pore gel material from the beaker and drying for 6 hours in the vacuum oven at the temperature of 50 ℃ to obtain the super-hydrophobic porous hydrogel.
Example 2
Taking polyvinyl alcohol with molecular weight of 80000-90000 as an example, firstly weighing sodium dodecyl sulfate with mass fraction of 1% (w/w), 1% (w/w) dextran (T-70), 15% (w/w) polyvinyl alcohol aqueous solution and 5% (w/w) gelatin according to a proportion, mixing the weighed materials into deionized water, putting the mixture into a magnetic stirring water pan, heating the mixture to 90 ℃, rapidly stirring the mixture for 3 hours by using a magnetic stirrer to rapidly dissolve the polyvinyl alcohol, the gelatin, the sodium dodecyl sulfate and the like, and then standing the mixture to normal temperature to obtain the required polymer solution; firstly, placing a microfluidic chip device, a polymer solution and a polymer liquid storage device in a 60-degree constant temperature box to reduce the viscosity of the polymer solution and increase the fluidity; injecting a polymer solution into a polymer solution storage bottle, respectively connecting a first Teflon hose 4 and a second Teflon hose 6 with the polymer solution storage bottle and an air storage bottle on a nitrogen pressure injection pump, and connecting a third Teflon hose 10 with a glass container 12 for micro-bubble collection; starting and adjusting a nitrogen pressure injection pump, pressing the polymer solution into a solution flow channel 5 through a first Teflon hose 4 and a solution inlet 3 and flowing at a high speed, pressing air into a gas flow channel 8 through a second Teflon hose 6 and a gas inlet 7 and flowing at a high speed, and cutting the gas in the fluid of the high-speed flowing polymer solution to quickly generate uniform liquid micro-bubbles; after a period of preparation, collecting the liquid microbubbles in a glass container for later use; freezing the liquid microbubbles collected in the glass container in freezing equipment with the freezing temperature of-20 ℃ for 12 hours, taking out the liquid microbubbles and placing the liquid microbubbles in a refrigerator with the melting temperature of 4 ℃ for 12 hours, and repeating the process twice; then, continuously freezing the materials for 12 hours at the freezing temperature of-20 ℃, storing the materials for 1 hour in a freezing device with the melting temperature of 4 ℃, storing the materials for 12 hours at the indoor temperature of 25 ℃, repeating the process twice, and crosslinking and solidifying the liquid polymer in the liquid microbubbles into the porous material wall, wherein the gas in the microbubbles is converted into a porous structure; removing water in the porous material by using a freeze dryer, pre-freezing the porous material at the temperature of-20 ℃, then gradually increasing the temperature from-20 ℃ to 20 ℃ in a step of 4 ℃ within the temperature range of-20 ℃ to 20 ℃, and obtaining a hydrophilic porous hydrogel material after 20 hours (as shown in figure 3); the primary polyvinyl alcohol pore gel material was immersed in a beaker of 3m Novec 7500 electronic fluorinated oil containing 5% o 1h,2 h-perfluorooctyltrichlorosilane by mass, heated in a vacuum oven at 50 ℃ for 12 hours, and then removed from the beaker and placed in a vacuum oven to dry at 50 ℃ for 6 hours to obtain a superhydrophobic porous hydrogel (see fig. 4).
The above embodiments are only for illustrating the embodiments of the present invention and not for limiting the embodiments of the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the embodiments of the present invention, so that all equivalent technical solutions also belong to the scope of the embodiments of the present invention, and the scope of patent protection of the embodiments of the present invention should be defined by the claims.

Claims (9)

1. A preparation method of a porous hydrogel based on a microbubble template is characterized by comprising the following steps:
A0. preparing a polymer solution; filling the prepared polymer solution into a polymer solution storage bottle;
A1. placing the microfluidic chip device, the polymer solution and the polymer solution storage bottle in a constant temperature box, preparing liquid micro bubbles by using the microfluidic chip device, and conveying the liquid micro bubbles to a low-temperature environment for collection and storage;
A2. through freeze thawing cycle induction, liquid polymers in the liquid microbubbles are crosslinked and solidified into porous material walls, and gas in the microbubbles is converted into the porous material;
A3. freeze-drying the porous material to remove water in the material, and preparing a hydrophilic primary polyvinyl alcohol pore gel material;
A4. and (3) chemically modifying the primary polyvinyl alcohol pore gel material, changing the original micro-nano structure, and forming a honeycomb structure on the pore wall to prepare the super-hydrophobic porous hydrogel.
2. The method for preparing a microbubble template-based porous hydrogel according to claim 1, wherein the step A0 of configuring the polymer solution is specifically performed by: the polymer solid reagent of polyvinyl alcohol, gelatin, dextran and sodium dodecyl sulfate is weighed according to a certain proportion and mixed into deionized water, and then the mixture is put into a magnetic stirring water pot and heated to 90 ℃, and the mixture is rapidly stirred for 3 hours by using a magnetic stirrer, so that the polyvinyl alcohol, the gelatin, the dextran and the sodium dodecyl sulfate are rapidly dissolved, and then the mixture is stood to normal temperature, and the needed polymer solution is obtained.
3. The method of claim 2, wherein the molecular weight of the polyvinyl alcohol is 80000 to 90000, the mass fraction is 15%, the mass fraction of dextran (T-70) is 1%, the mass fraction of gelatin is 5%, and the mass fraction of sodium dodecyl sulfate is 1%.
4. The method for preparing porous hydrogel based on microbubble template as claimed in claim 1, wherein the microfluidic chip device comprises a glass substrate (1), a microchannel system (2) having a specific microchannel structure is bonded on the glass substrate (1); the microchannel system (2) comprises a solution flow channel (5) and a gas flow channel (8), wherein the inlet end of the solution flow channel (5) is a solution inlet (3), the outlet end of the solution flow channel (5) is communicated with a solution outlet (11) through a snake-shaped flow channel (9), the inlet end of the gas flow channel (8) is a gas inlet (7), and the outlet end of the gas flow channel (8) is communicated with the middle part of the solution flow channel (5); the solution inlet (3) is connected with one end of a first Teflon hose (4), the other end of the first Teflon hose (4) is connected with a polymer solution storage bottle, the gas inlet (7) is connected with one end of a second Teflon hose (6), the other end of the second Teflon hose (6) is connected with an air storage bottle, the polymer solution storage bottle and the air storage bottle are both connected with a nitrogen pressure injection pump, the solution outlet (11) is connected with one end of a third Teflon hose (10), and the other end of the third Teflon hose (10) extends into a glass container (12); the micro-channel system (2) is made of polydimethylsiloxane.
5. The method for preparing the microbubble template-based porous hydrogel according to claim 4, wherein the step A1 of preparing the liquid microbubbles based on the microfluidic chip device comprises the following specific operations: firstly, placing a microfluidic chip device, a polymer solution and a polymer solution storage bottle in a 60-DEG thermostat, and placing a glass container (12) in a zero-temperature low-temperature environment; starting a nitrogen pressure injection pump, adjusting proper pressure, and pressing the polymer solution in the polymer solution storage bottle and the gas in the air storage bottle into the solution flow passage (5) and the gas flow passage (8) respectively through the first Teflon hose (4) and the second Teflon hose (6) and flowing at high speed; the gas in the gas flow passage (8) rapidly generates uniform micro-bubbles under the fluid shear of the high-speed flowing polymer solution in the solution flow passage (5), and finally flows into the glass container (12) through the third Teflon hose (10) for collection.
6. The method of claim 5, wherein the gas is air or nitrogen.
7. The method for preparing a porous hydrogel based on a microbubble template as claimed in claim 1, wherein the specific operation procedures induced by the freeze-thaw cycle in the step A2 are as follows:
a21: freezing the liquid microbubbles collected in the glass container (12) in a freezing device with freezing temperature of-20 ℃ for 12 hours, and then taking out and placing in a refrigerator with melting temperature of 4 ℃ for 12 hours;
a22: repeating A21 again;
a23: continuing to freeze the material after A22 at-20 deg.C for 12 hr, storing in a freezing device with 4 deg.C for 1 hr, and storing at room temperature of 25 deg.C for 12 hr;
a24: repeating A23 again to obtain a preliminarily gelled porous hydrogel material.
8. The method for preparing a porous hydrogel based on a microbubble template as claimed in claim 1, wherein the specific operation procedure of the step A3 is as follows: removing water in the porous hydrogel material by using a freeze dryer, pre-freezing the preliminarily gelled porous hydrogel material at the temperature of-20 ℃, and then gradually heating from-20 ℃ to 20 ℃ in a step of 4 ℃ within the temperature range of-20 ℃ to 20 ℃; after 20 hours, a hydrophilic primary polyvinyl alcohol pore gel material was obtained.
9. The method for preparing a porous hydrogel based on a microbubble template as claimed in claim 1, wherein the specific operation procedure of the step A4 is as follows: immersing the primary polyvinyl alcohol pore gel material in a beaker containing 3M Novec 7500 electronic fluorinated oil with the mass fraction of 5 thousandths 1H,2H and 2H-perfluorooctyltrichlorosilane, heating for 12 hours in a vacuum oven with the set temperature of 50 ℃, and then taking out the primary polyvinyl alcohol pore gel material from the beaker and drying for 6 hours in the vacuum oven at the temperature of 50 ℃ to obtain the super-hydrophobic porous hydrogel.
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