CN113214533A - Shape memory porous material and preparation method and application thereof - Google Patents
Shape memory porous material and preparation method and application thereof Download PDFInfo
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- CN113214533A CN113214533A CN202110474420.3A CN202110474420A CN113214533A CN 113214533 A CN113214533 A CN 113214533A CN 202110474420 A CN202110474420 A CN 202110474420A CN 113214533 A CN113214533 A CN 113214533A
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- shape memory
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention relates to the field of shape memory materials, in particular to a shape memory porous material and a preparation method and application thereof. The invention provides a shape memory porous material, and a preparation method of the shape memory porous material comprises the following steps: physically adhering the coating material and the porous material substrate; the coating material is a shape memory polymer. The shape memory sponge has the advantages of simple preparation method, and easily adjustable structure and performance; the prepared shape memory porous material has the advantages of shape memory property, large volume change, good biocompatibility and no toxicity to human bodies, and can be widely applied to the fields of medical care, textile and clothing, catalysis, aerospace, unmanned driving, heat insulation foam, oil stain absorption or dust particle absorption and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a shape memory porous material and a preparation method and application thereof.
Background
Shape Memory Polymers (SMPs) are the most typical member of the smart material family. The polymer is a polymer which has a certain initial shape, is deformed and fixed under a certain external action, and can restore the original shape through external condition stimulation such as light, electricity, heat, chemical condition change (pH value, chelating reaction and phase transition) and the like. Because of the special performance, the SMPs have wide application range, are small as food utensils in daily life, and are large as the fields of engineering application, aerospace, biomedical, intelligent textile, sensing display devices, automatic control systems and the like. Especially, the artificial muscle, the artificial skin, the automatic drug delivery system, the surgical suture, the stent, the heart valve (bionic membrane), the tissue engineering and the like are reported as medical materials at present. Compared to conventional Shape Memory Alloys (SMA) and Shape Memory Ceramics (SMC), SMPs have the following advantages: the rubber has high elasticity and good recoverability; the structure is high in designability and adjustable, the recovery temperature can be adjusted by a chemical method, the recovery behavior can be controlled, and multiple response memory, multiple temperature areas and multiple shapes are easy to realize; (3) the preparation is simple, the raw materials are wide, and the price is low; (4) the molding processing is easy, and the material with a complex structure is easy to obtain; (5) the material has better biocompatibility and can be naturally degraded; sixthly, low density and the like.
Currently, there are many appliances or seals on the market, requiring large volume changes; therefore, the shape memory foam or sponge material has better application prospect. However, the conventional foam or sponge preparation method is prepared by chemical foaming, the process is complex, the product quality is not easy to control, especially the shape memory polymer with wet response is easy to absorb moisture, and functional groups are easy to embed in the chemical foaming process to influence the moisture absorption function and response speed. Therefore, the development of a novel wet response shape memory foam material to improve the wet response shape memory performance is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of complex preparation process of shape memory foam or sponge material in the prior art, and provides a shape memory porous material, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a shape memory porous material, and a preparation method of the shape memory porous material comprises the following steps: physically adhering the coating material and the porous material substrate; the coating material is a shape memory polymer.
Optionally, the preparation method of the shape memory porous material specifically comprises the following steps:
1) the porous material substrate is put into a shape memory polymer solution with the concentration of 1-40 wt% to be soaked for 1-30 minutes (the solution is allowed to permeate into the sponge).
Optionally, the method further comprises step 2): the porous material to which the shape memory polymer solution is adhered is subjected to a drying process.
Optionally, the method further includes, between step 1) and step 2): and taking out the porous material soaked with the shape memory polymer solution, and standing at 25 +/-2 ℃ for 1-30 minutes to separate out the redundant shape memory polymer solution, thereby obtaining the porous material adhered with the shape memory polymer solution.
Optionally, the drying treatment is a thermal drying treatment or a freeze drying treatment;
optionally, the conditions of the thermal drying treatment are as follows: placing a sample to be dried in an oven at 50-100 ℃ for more than 24 h;
optionally, the conditions of the freeze drying treatment are as follows: freezing the sample to be dried in a cold trap at-60-10 ℃ for more than 24 hours.
The sample to be dried is a porous material to which a shape memory polymer solution is adhered.
Optionally, the material of the porous material substrate is selected from one or more of cotton, wool, hemp, wood fiber or foamed plastic polymer; optionally, the material of the porous material substrate is soft polyurethane foam, ethylene-vinyl acetate foam and/or rubber cotton; optionally, the porous material substrate is a sponge, and the sponge has good elasticity.
The shape memory sponge prepared by the method has an open pore structure and can quickly absorb moisture; the wet response shape memory polymer is mainly adhered to the surface layer of the sponge structure, has small dosage and high wet response speed, and can quickly absorb moisture or recover the shape at high temperature.
The shape memory polymer has a moisture responsive shape memory property and/or a heat responsive shape memory property; one or more selected from a shape memory polymer of a polyethylene glycol system (optionally, a shape memory polymer of a polyethylene glycol system prepared by an invention patent with an application number of CN201580074457.X, such as TPEG20), a zwitterionic shape memory polymer (optionally, a zwitterionic shape memory polymer prepared by an invention patent with an application number of CN 201410720521.4), a betaine type shape memory polymer (optionally, a betaine type shape memory polymer prepared by an invention patent with an application number of CN201410357273.1, and an invention patent example 1 prepared by an invention patent with an application number of CN201915307526. X, such as betaine type shape memory polyurethane, optionally, pyridine betaine type shape memory polyurethane), an acrylic acid shape memory polymer and a polyvinyl alcohol shape memory polymer;
optionally, the solvent of the shape memory polymer solution is selected from water, toluene, ethyl acetate, ethanol, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, and/or dimethylsulfoxide.
The shape memory porous material (sponge) can be deformed into another shape or compressed into a temporary shape with a smaller volume under the action of external thermal stimulation (50-100 ℃), the shape can be stabilized and not changed after being sealed and stored, but the temporary shape can be quickly recovered to the original shape when being placed in a wet environment or a water-containing environment.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a shape memory porous material, the preparation method of the shape memory porous material is simple (synthesis is adopted in the prior art instead of physical adhesion), and the structure and the performance are easy to regulate and control (the structure and the performance can be regulated and controlled by selecting a shape memory polymer, preparing the concentration of the shape memory polymer and the like); the prepared shape memory porous material (sponge) has the characteristics of wet response (thermal response) shape memory, large volume change, good biocompatibility and no toxicity to human bodies, and can be widely applied to the fields of medical care, textile and clothing, catalysis, aerospace and the like; can be used as a high-efficiency hemostatic sponge and has application potential in the fields of sealing and storing of oil wells or geothermal wells and the like.
2. The invention provides a shape memory porous material, which can realize biodegradation performance by selecting biodegradable foam as a porous material substrate, and can realize good biocompatibility by selecting a substrate with good biocompatibility and a shape memory polymer.
3. The shape memory porous material provided by the invention has a shape memory function, has larger volume deformation, can be circularly compressed, and still keeps complete structure;
4. the shape memory porous material provided by the invention has the characteristics of high wet response speed, high recovery speed and the like.
5. The shape memory porous material prepared by the invention can be used for blood vessel occlusion devices, can also be used for intelligent products such as blood absorption cotton, automatic water absorption cotton, automatic moisture absorption cotton and the like, and has automatically changed adsorption capacity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a sponge of example 1 of the present invention impregnated with a shape memory polymer solution;
FIG. 2 is a comparison of shape memory sponge (left) and sponge stock (right) after drying treatment according to example 1 of the present invention;
FIG. 3 is a sample of a shape memory sponge after drying treatment according to example 2 of the present invention;
FIG. 4 is a diagram of the shape memory sponge sample compressed at 50 ℃ according to the embodiment 2 of the present invention, wherein the shape of the compressed shape can be fixed under the room temperature sealing condition;
FIG. 5 is a diagram of a shape memory sponge according to example 3, which is compressed at 50 ℃ and sealed at room temperature to fix its shape after being compressed;
FIG. 6 shows that the shape-memory sponge of example 3 of the present invention can be restored to its original shape after being left for 5 hours under 80% RH;
FIG. 7 is a diagram of a shape memory sponge according to example 4, which is compressed at 50 ℃ and sealed at room temperature, and then the shape of the shape memory sponge is fixed;
FIG. 8 shows that the shape-memory sponge of example 4 of the present invention can be restored to its original shape after being deformed and left in water for 10 minutes.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
1. The preparation method of the zwitterionic shape memory polymer is disclosed in patent example 1 which is already granted under the application number CN201410720521.4, so that the shape memory polymer with good biocompatibility and wet response shape memory characteristics is obtained; the zwitterionic shape memory polymer was then polymerized using DMF: dissolving the mixed solvent with the water volume ratio of 5:5 to obtain a 1 wt% zwitterionic shape memory polymer solution.
2. Soaking sponge in zwitterionic shape memory polymer solution for 10 min, and taking out the sponge soaked with the shape memory polymer solution, as shown in FIG. 1; suspending the mixture at room temperature for 10 minutes to allow the excess solution to flow out; then, processing the sponge for 36 hours at the temperature of minus 40 ℃ by using freeze drying equipment to obtain the shape memory sponge; the comparison of the dried sample (shape memory sponge) with the sponge material is shown in FIG. 2, which clearly shows that the dried sponge has a large amount of polymer adhered thereto.
Example 2
1. The hydrophilic shape memory polymer is prepared by the method disclosed in patent example 1 of the invention with the application number of CN201580074457.X, and the hydrophilic shape memory polymer (TPEG 20) is prepared; then heating and dissolving the hydrophilic shape memory polymer by water to obtain a shape memory polymer solution with the concentration of 40 wt%;
2. soaking the sponge in the shape memory polymer solution for 5 minutes, and then taking out the sponge soaked with the shape memory polymer solution; suspending the mixture at room temperature for 5 minutes to allow the excess solution to flow out; then processing the sponge for 24 hours by using vacuum drying equipment at 50 ℃ to obtain the shape memory sponge;
3. the dried sample (shape memory sponge) has a fluffy porous structure and a large volume, as shown in fig. 3; but under the condition of 50 ℃, the shape of the compressed volume can be fixed under the condition of room temperature and sealing conditions by the compression of the volume (a deformation mode), and as shown in figure 4, the shape fixing performance is good. When the temperature is heated to 50 ℃ again, the material can be quickly recovered to the original shape, good thermal response shape recovery performance is shown, and the material can be recovered to the original shape after being placed in water for 10 minutes.
Example 3
1. The preparation method of the shape memory polymer is shown in patent example 1 of the invention with the granted application number of CN201410357273.1, a betaine type shape memory polymer (the shape memory polymer based on DMAPS-AA) is prepared, and then the shape memory polymer is dissolved by water to obtain a shape memory polymer solution with the concentration of 20 wt%;
2. soaking the sponge in the shape memory polymer solution for 8 minutes, and then taking out the sponge soaked with the shape memory polymer solution; suspending the mixture at room temperature for 5 minutes to allow the excess solution to flow out; then the shape memory sponge is obtained after the treatment for 36 hours at the temperature of 40 ℃ below zero by using freeze drying equipment.
3. After the shape memory sponge is subjected to volume compression (a deformation processing mode) at 50 ℃, the shape of the shape memory sponge can be fixed after the volume compression at room temperature and under a sealed condition, as shown in fig. 5; but can be restored to the original shape after being left for 5 hours under the condition of 80% RH, as shown in fig. 6, and the shape-memory sponge shows good shape-memory effect.
Example 4
1. The preparation method of the shape memory polymer is disclosed in patent example 1 of the invention with the application number of CN201910753526.X, which is granted to prepare betaine type shape memory polyurethane (pyridine betaine shape memory polyurethane); the shape memory polymer was then dissolved in dimethyl sulfoxide to give a 30 wt% solution of the shape memory polymer.
2. Soaking the sponge in the shape memory polymer solution for 8 minutes, and then taking out the sponge soaked with the shape memory polymer solution; suspending the mixture at room temperature for 5 minutes to allow the excess solution to flow out; then the shape memory sponge is obtained after the treatment for 36 hours at the temperature of 40 ℃ below zero by using freeze drying equipment.
3. After the shape memory sponge is subjected to volume compression (a deformation processing mode) at 50 ℃, the shape of the shape memory sponge can be fixed at room temperature under the condition of sealing conditions after the volume compression, as shown in fig. 7; but when left in water for 10 minutes, it returns to its original shape, as shown in fig. 8, and the shape-memory sponge shows a good water-responsive shape-memory effect.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A shape memory porous material, characterized in that,
the preparation method of the shape memory porous material comprises the following steps: physically adhering the coating material and the porous material substrate; the coating material is a shape memory polymer.
2. Shape memory porous material according to claim 1,
the method specifically comprises the following steps:
1) putting the porous material base material into a shape memory polymer solution with the concentration of 1-40 wt% to soak for 1-30 minutes; optionally, soaking for 1-10 minutes.
3. Shape memory porous material according to claim 1 or 2,
the method further comprises step 2): the porous material to which the shape memory polymer solution is adhered is subjected to a drying process.
4. Shape memory porous material according to any of claims 1 to 3,
the method also comprises the following steps between the step 1) and the step 2): and taking out the porous material soaked with the shape memory polymer solution, and standing at 25 +/-2 ℃ for 1-30 minutes to separate out the redundant shape memory polymer solution to obtain the porous material adhered with the shape memory polymer solution.
5. Shape memory porous material according to claim 3,
the drying treatment is thermal drying treatment or freeze drying treatment;
optionally, the conditions of the thermal drying treatment are as follows: placing a sample to be dried in an oven at 50-100 ℃ for more than 24 h;
optionally, the conditions of the freeze drying treatment are as follows: freezing a sample to be dried in a cold trap at the temperature of-60-10 ℃ for more than 24 hours;
the sample to be dried is a porous material to which a shape memory polymer solution is adhered.
6. Shape memory porous material according to any of claims 1 to 5,
the material of the porous material substrate is selected from one or more of cotton, wool, hemp, wood fiber or foamed plastic polymer; optionally, the material of the porous material substrate is soft polyurethane foam, ethylene-vinyl acetate foam and/or rubber cotton; optionally, the porous material substrate is a sponge;
the shape memory polymer is one or more selected from polyethylene glycol system shape memory polymer, zwitterionic shape memory polymer, betaine type shape memory polymer, acrylic acid shape memory polymer and polyvinyl alcohol shape memory polymer.
7. Shape memory porous material according to any of claims 2 to 6, characterized in that the solvent of the shape memory polymer solution is selected from water, toluene, ethyl acetate, ethanol, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and/or dimethylsulfoxide.
8. A method of preparing a shape memory porous material as claimed in any one of claims 1 to 7.
9. Use of the shape memory porous material according to any one of claims 1 to 7 in the fields of healthcare, textile clothing, catalysis, aerospace.
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| CN202110474420.3A CN113214533A (en) | 2021-04-29 | 2021-04-29 | Shape memory porous material and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213848A (en) * | 2021-12-28 | 2022-03-22 | 南京航空航天大学 | Shape memory porous material capable of being shaped at body temperature/room temperature and preparation method thereof |
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2021
- 2021-04-29 CN CN202110474420.3A patent/CN113214533A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 刘鹏昌等: ""超浸润形状记忆海绵的制备及油-水分离性能"", 《高等学校化学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213848A (en) * | 2021-12-28 | 2022-03-22 | 南京航空航天大学 | Shape memory porous material capable of being shaped at body temperature/room temperature and preparation method thereof |
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