CN110938273A - Self-repairing composite material with polarization patterning capability and preparation method thereof - Google Patents

Self-repairing composite material with polarization patterning capability and preparation method thereof Download PDF

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CN110938273A
CN110938273A CN201911121297.6A CN201911121297A CN110938273A CN 110938273 A CN110938273 A CN 110938273A CN 201911121297 A CN201911121297 A CN 201911121297A CN 110938273 A CN110938273 A CN 110938273A
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CN110938273B (en
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徐丽容
洪炜
陈旭东
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Sun Yat Sen University
National Sun Yat Sen University
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Abstract

The invention discloses a preparation method and application of a self-repairing composite material with polarization patterning capability. The preparation method of the polymer material comprises the following steps: dissolving a polymer monomer in a solvent, uniformly mixing, adding an initiator, and carrying out polymerization reaction under an oxygen-free condition to obtain a copolymer; adding the nano metal into the copolymer, heating and uniformly mixing to obtain a nano metal polymer; will contain Fe3+Dissolving the inorganic salt in polybasic acid, adjusting pH, adding into the nano metal polymer, heating and mixing uniformly to obtain the product with polarization patterning energyForce nanometal polymer composites. The prepared nano metal polymer composite material with polarization patterning capability has important application value and prospect in the fields of patterning, pattern hiding, optical encryption anti-counterfeiting and 3D printing.

Description

Self-repairing composite material with polarization patterning capability and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a self-repairing composite material with polarization patterning capability and a preparation method thereof.
Background
The metal nano polymer composite material has been applied in many fields due to excellent physical and chemical properties, and the metal nano particles are dispersed in a polymer matrix, so that the properties of the metal nano particles and the properties of the polymer can be organically combined together, the electromagnetic property, the optical property, the catalytic property, the sensing property and the like of the nano composite material are enhanced, and the novel application of the nano composite material in the field of functional materials is started. The mechanical, optical, electrical and magnetic properties of the metal nanocomposite depend not only on the properties of the compositions, but also on the structure of the metal nanocomposite and the arrangement of the metal nanoparticles in the copolymer domains. The surface plasmon resonance optical properties of metallic nanoparticles are related to the shape of the nanoparticle and the dielectric constant of the surrounding medium in which it is located. The spherical metal nanoparticles only show one plasma absorption peak due to the structural symmetry, and different from the spherical metal nanoparticles, the metal nanorods show two plasma resonance modes due to the structural anisotropy: transverse plasmon resonance (TSPR) and longitudinal plasmon resonance (LSPR). In an oriented nanometal polymer composite, the nanometal polymer composite may exhibit polarization optical properties: when the axial direction of the metal nano-rod is parallel to the polarization direction of light, the LSPR can be completely excited; in contrast, when the vertical axis direction of the metal nanorods is parallel to the polarization direction of light, the LSPR is suppressed.
In order to achieve efficient excitation of metal nanorods LSPR in the material, the material with enhanced Properties of metal nanorods by using a heat-spun method, a spinning method and the like is studied [ Jean-Michell Lamarre, Franck Billard, Chahineze Harkati Kerboua, Michel Lequime, Sjoerd Roorda, & Ludvik Martinu. Although many researches on the polarization optical characteristics of metal nano-materials are currently carried out, the application fields of the metal nano-materials are quite limited, and the application of the metal nano-composite materials with the polarization optical characteristics to patterning, 3D printing and optical encryption anti-counterfeiting has not been reported.
Therefore, it is urgent to find a self-repairing nano metal polymer composite material with polarization patterning capability to realize applications in the fields of patterning, 3D printing, optical encryption anti-counterfeiting and the like, so as to expand the application range of the metal nano composite material.
Disclosure of Invention
The invention aims to provide a self-repairing nano metal polymer composite material with polarization patterning capability and a preparation method thereof. The self-repairing nano metal polymer composite material prepared by the preparation method can realize polarization patterning and shielding and hiding of patterns, thereby realizing application in the field of optical encryption anti-counterfeiting. In addition, the composite material can be used in 3D printing, and patterns printed by 3D printing also have polarization characteristics. The self-repairing performance of the material can realize the continuous development and the recycling of the material.
The invention aims to provide a preparation method of a self-repairing composite material with polarization patterning capability.
It is another object of the present invention to provide a self-healing composite material with polarization patterning capability.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of a self-repairing composite material with polarization patterning capability comprises the following steps:
s1: dissolving a polymer monomer A and a polymer monomer B in a solvent, uniformly mixing, adding an initiator, and carrying out polymerization reaction under an oxygen-free condition to obtain a copolymer;
s2: adding the nano metal into the copolymer obtained in the step S1, heating and uniformly mixing to obtain a nano metal polymer;
s3: will contain Fe3+The inorganic salt of (A) is dissolved in a plurality of elementsIn acid, adjusting the pH value to 2-5, adding the solution into the nano metal polymer obtained in the step S2, heating and uniformly mixing to obtain a self-repairing composite material with polarization patterning capability;
the polymer monomer A is one or more of acrylic acid, acrylic acid derivatives, methyl acrylate derivatives, methacrylic acid derivatives, methyl methacrylate and methyl methacrylate derivatives;
the polymer monomer B is 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate.
Preferably, the solvent is one or more of water, methanol and ethanol.
Preferably, the initiator is one or two of 2-20% of ammonium persulfate and 2-20% of potassium persulfate.
Preferably, the nano metal is one or more of gold nanorods, silver nanorods and platinum nanorods.
Preferably, the Fe-containing compound3+The inorganic salt is one or more of ferric chloride, ferric sulfate and ferric nitrate.
Preferably, the polybasic acid is one or more of citric acid, tartaric acid and oxalic acid.
Preferably, the pH is adjusted to 3-4 in step S2.
Preferably, the polymer monomer A, the polymer monomer B, the solvent, the initiator, the nano metal and the Fe-containing material3+The inorganic salt and the polybasic acid have the following weight part ratio: 5-50: 5-50: 0-90: 0.1-3: 0.1-1: 0.01-5: 0.01 to 5.
More preferably, the polymer monomer A, the polymer monomer B, the solvent, the initiator, the nano metal and the Fe-containing material3+The inorganic salt and the polybasic acid have the following weight part ratio: 8.5-21.5: 8.5-21.5: 70-80: 0.1-3: 0.3-0.5: 0.05-0.1: 0.25 to 0.5.
Further preferably, the polymer monomer A, the polymer monomer B, the solvent, the initiator, the nano metal and the Fe-containing material3+The inorganic salt and the polybasic acid have the following weight part ratio: 8.5: 21.5: 70: 0.3：0.3：0.05：0.25。
Preferably, the length-diameter ratio of the gold nanorods, the silver nanorods and the platinum nanorods is 2-4.7.
Preferably, the oxygen-free condition in step S1 is to introduce nitrogen into the system.
Preferably, the temperature of the polymerization reaction in the step S1 is 65-75 ℃, and the time of the polymerization reaction is 6-12 h.
Most preferably, the temperature of the polymerization reaction in the step S1 is 70 ℃, and the time of the polymerization reaction is 10 h.
Preferably, the temperature for heating and uniformly mixing in the steps S2 and S3 is 60-100 ℃.
More preferably, the temperature for heating and uniformly mixing in the steps S2 and S3 is 80-90 ℃; most preferably 80 deg.c.
The invention also protects the self-repairing composite material with polarization patterning capability prepared by the method.
The self-repairing nano metal polymer composite material prepared by the invention is applied to polarization patterning, has the functions of pattern hiding and encryption anti-counterfeiting, is applied to 3D printing, and has polarization property directly.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the preparation process of the self-repairing nano metal polymer composite material, nano metal is arranged and oriented in the polymer, so that the nano metal polymer composite material shows polarization optical characteristics.
(2) The preparation method has simple process and mild and controllable conditions, can produce the nano metal polymer composite material with excellent polarization optical characteristics, can realize self-repairing, and is suitable for sustainable development and use in the field of high polymer materials.
(3) The self-repairing nano metal polymer composite material prepared by the invention can realize polarization patterning, and can realize shielding and hiding of patterns while patterning, thereby realizing application in the field of optical encryption anti-counterfeiting; the composite material can be used for 3D printing, and the printed patterns also have polarization characteristics.
Drawings
FIG. 1 is a polarization spectrum of a self-healing nano-metal polymer composite;
FIG. 2 is a graph of the patterning effect of a self-healing nano-metal polymer composite;
FIG. 3 is a rheological diagram of a self-healing nano-metal polymer composite;
FIG. 4 is a self-healing flow diagram of a self-healing nano-metal polymer composite;
FIG. 5 is a 3D printing effect diagram of a self-healing nano-metal polymer composite;
FIG. 6 is an infrared hidden pattern of a self-healing nano-metal polymer composite;
FIG. 7 is a diagram showing different number-letter effects of the self-repairing nano metal polymer composite material under infrared photo-thermal conditions.
Detailed Description
The present invention will be described in further detail with reference to the drawings and specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
The parts appearing in the following examples are parts by weight.
Example 1
1. Preparation method
S1: 8.5 parts of methacrylic acid and 21.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate are dissolved in 70 parts of water and uniformly mixed, 0.3 part of 10 percent initiator ammonium persulfate is added, and polymerization reaction is carried out for 10 hours at 70 ℃ under the condition of introducing nitrogen gas, so as to obtain the copolymer.
S2: and (3) adding 0.3 part of gold nanorod with the length-diameter ratio of 2.0 into the copolymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.05 part of ferric chloride and 0.25 part of citric acid in 6 parts of water, adjusting the pH value to 3, adding the solution into the nano metal rod polymer prepared in the step S2, heating to 80 ℃, and uniformly mixing to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
(1) Optical characteristics of polarization
As shown in FIG. 1, after the nano-metal rod polymer of the present invention is stretched, the absorption peak intensities will be significantly different in different polarized light directions (along the axial and vertical axes), which is caused by the polarization effect generated by the alignment of the nano-gold rods in the polymer.
(2) Polarization patterning
When local depolarization is performed, the nano metal polymer can be made to show different patterns, as shown in fig. 2, under polarized light, patterns more obvious than under natural light can be observed, and the colors of different polarization directions are different.
Example 2
1. Preparation method
S1: 8.5 parts of methyl methacrylate and 21.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate are dissolved in 70 parts of water and uniformly mixed, 0.3 part of 10 percent initiator potassium persulfate is added, and polymerization reaction is carried out for 10 hours at 70 ℃ under the condition of introducing nitrogen gas, thus obtaining the copolymer.
S2: and (3) adding 0.3 part of gold nanorod with the length-diameter ratio of 3.0 into the polymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.05 part of ferric chloride and 0.25 part of citric acid in 6 parts of water, adjusting the pH value to 3, adding the solution into the nano gold rod polymer prepared in the step S2, heating the solution to 80 ℃, and uniformly mixing the solution to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
(1) Self-repairing
As shown in FIG. 3, when the nano metal rod polymer of the present invention is subjected to a rheological test, the storage modulus and the loss modulus are crossed at 68 ℃, which shows that the nano metal rod polymer of the present invention has a gel-sol transition at this temperature, and can realize self-repair. As shown in FIG. 4, two segments of the nano metal rod polymer of the invention are spliced together to realize self-repair, and the repaired nano metal rod polymer can be re-stretched and does not break at the splicing opening.
(2)3D printing
The nano metal rod polymer can be used for 3D printing, and can be printed into any shape according to programming codes, as shown in figure 5, grids and flowers are printed out by the nano metal rod polymer, wherein a is the grids, and the horizontal stripes and the vertical stripes under different polarized light are different in color; b is a flower which can display different colors in different polarization directions.
Example 3
1. Preparation method
S1: 8.5 parts of methacrylic acid and 21.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate are dissolved in 70 parts of water and uniformly mixed, 0.3 part of 10 percent initiator ammonium persulfate is added, and polymerization reaction is carried out for 10 hours at 70 ℃ under the condition of introducing nitrogen gas, so as to obtain the copolymer.
S2: and (3) adding 0.3 part of gold nanorod with the length-diameter ratio of 4.7 into the polymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.1 part of ferric chloride and 0.5 part of citric acid in 6 parts of water, adjusting the pH value to 3, adding the solution into the nano gold rod polymer prepared in the step S2, heating the solution to 80 ℃, and uniformly mixing the solution to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
(1) Pattern hiding
The nano gold rod prepared by the method has the absorption wavelength of about 880 nm. When the concentration of the nano gold rod is low enough, the pattern of the nano metal rod polymer can not be observed by naked eyes, and the pattern on the nano metal rod polymer can be shot by using an infrared camera. As shown in fig. 6, the letter "SYSU" is not observed with the naked eye under natural light, whereas the letter "SYSU" is observed under infrared light, and the masking and hiding of the pattern can be achieved.
(2) Infrared photothermographic imaging
The nano gold rod prepared by the method can absorb infrared light to generate heat, the heat is different in different polarization directions, and by utilizing the property that the nano gold rod generates heat in different polarization directions and has temperature difference, the nano gold rod polymer can realize the display of different patterns, as shown in figure 7.
Example 4
1. Preparation method
S1: dissolving 21.5 parts of methacrylic acid and 8.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate in 80 parts of water, uniformly mixing, adding 0.3 part of 10% initiator ammonium persulfate, and carrying out polymerization reaction for 10 hours at 70 ℃ under the condition of introducing nitrogen to obtain the copolymer.
S2: and (3) adding 0.3 part of gold nanorod with the length-diameter ratio of 2.0 into the polymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.05 part of ferric chloride and 0.25 part of citric acid in 6 parts of water, adjusting the pH value to 3, adding the solution into the nano gold rod polymer prepared in the step S2, heating the solution to 80 ℃, and uniformly mixing the solution to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
The results of the analytical tests of the nano metal rod polymers prepared by the above methods according to the methods of examples 1 to 3 show that the nano gold rod polymer composite materials prepared by the method also have the self-repairing and polarization patterning properties described above.
Example 5
1. Preparation method
S1: dissolving 21.5 parts of methacrylic acid and 8.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate in 70 parts of water, uniformly mixing, adding 0.7 part of 5% potassium persulfate as an initiator, and carrying out polymerization reaction for 10 hours at 70 ℃ under the condition of introducing nitrogen to obtain the copolymer.
S2: and (3) adding 0.3 part of gold nanorod with the length-diameter ratio of 2.0 into the polymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.05 part of ferric sulfate and 0.25 part of citric acid in 6 parts of water, adjusting the pH value to 3, adding the solution into the nano gold rod polymer prepared in the step S2, heating the solution to 80 ℃, and uniformly mixing the solution to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
The results of the analytical tests of the nano metal rod polymers prepared by the above methods according to the methods of examples 1 to 3 show that the nano gold rod polymer composite materials prepared by the method also have the self-repairing and polarization patterning properties described above.
Example 6
1. Preparation method
S1: 8.5 parts of acrylic acid and 21.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate are dissolved in 80 parts of ethanol and uniformly mixed, 0.3 part of 10% initiating agent ammonium persulfate is added, and polymerization reaction is carried out for 10 hours at 70 ℃ under the condition of introducing nitrogen gas, so as to obtain the copolymer.
S2: and (3) adding 0.3 part of gold nanorod with the length-diameter ratio of 2.0 into the polymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.05 part of ferric chloride and 0.25 part of citric acid in 6 parts of water, adjusting the pH value to 3, adding the solution into the nano gold rod polymer prepared in the step S2, heating the solution to 90 ℃, and uniformly mixing the solution to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
The results of the analytical tests of the nano metal rod polymers prepared by the above methods according to the methods of examples 1 to 3 show that the nano gold rod polymer composite materials prepared by the method also have the self-repairing and polarization patterning properties described above.
Example 7
1. Preparation method
S1: dissolving 8.5 parts of methyl acrylate and 21.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate in 80 parts of methanol, uniformly mixing, adding 0.3 part of 10% initiator ammonium persulfate, and carrying out polymerization reaction for 10 hours at 70 ℃ under the condition of introducing nitrogen to obtain the copolymer.
S2: and (3) adding 0.3 part of gold nanorod with the length-diameter ratio of 2.0 into the polymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.05 part of ferric nitrate and 0.25 part of oxalic acid in 6 parts of water, adjusting the pH value to 4, adding the solution into the nano gold rod polymer prepared in the step S2, heating the solution to 90 ℃, and uniformly mixing the solution to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
The results of the analytical tests of the nano metal rod polymers prepared by the above methods according to the methods of examples 1 to 3 show that the nano gold rod polymer composite materials prepared by the method also have the self-repairing and polarization patterning properties described above.
Example 8
1. Preparation method
S1: 8.5 parts of methacrylic acid and 21.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate are dissolved in 80 parts of ethanol and uniformly mixed, 0.3 part of 5 percent initiator ammonium persulfate is added, and polymerization reaction is carried out for 10 hours at 70 ℃ under the condition of introducing nitrogen gas, so as to obtain the copolymer.
S2: and (3) adding 0.3 part of gold nanorod with the length-diameter ratio of 2.0 into the polymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.1 part of ferric nitrate and 0.5 part of tartaric acid in 6 parts of water, adjusting the pH value to 3, adding the solution into the nano gold rod polymer prepared in the step S2, heating the solution to 80 ℃, and uniformly mixing the solution to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
The results of the analytical tests of the nano metal rod polymers prepared by the above methods according to the methods of examples 1 to 3 show that the nano gold rod polymer composite materials prepared by the method also have the self-repairing and polarization patterning properties described above.
Example 9
1. Preparation method
S1: 8.5 parts of methacrylic acid and 21.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate are dissolved in 70 parts of methanol and uniformly mixed, 0.3 part of 10 percent initiator potassium persulfate is added, and polymerization reaction is carried out for 10 hours at 70 ℃ under the condition of introducing nitrogen gas, thus obtaining the copolymer.
S2: and (3) adding 0.3 part of silver nanorod with the length-diameter ratio of 2.0 into the polymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.05 part of ferric nitrate and 0.25 part of citric acid in 6 parts of water, adjusting the pH value to 3, adding the solution into the nano silver rod polymer prepared in the step S2, heating the solution to 80 ℃, and uniformly mixing the solution to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
The results of the analytical tests of the nano metal rod polymers prepared by the methods according to examples 1 to 3 show that the nano silver rod polymer composite materials prepared by the methods also have the self-repairing and polarization patterning properties.
Example 10
1. Preparation method
S1: 8.5 parts of methacrylic acid and 21.5 parts of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate are dissolved in 70 parts of water and uniformly mixed, 0.5 part of 10 percent initiator potassium persulfate is added, and polymerization reaction is carried out for 10 hours at 70 ℃ under the condition of introducing nitrogen gas, thus obtaining the copolymer.
S2: and (3) adding 0.5 part of platinum nanorod with the length-diameter ratio of 2.0 into the polymer prepared in the step S1, heating to 80 ℃, and uniformly mixing to obtain the nano metal polymer.
S3: dissolving 0.1 part of ferric sulfate and 0.5 part of citric acid in 6 parts of water, adjusting the pH value to 4, adding the solution into the nano platinum rod polymer prepared in the step S2, heating the solution to 90 ℃, and uniformly mixing the solution to obtain the self-repairing composite material with polarization patterning capability.
2. Analysis of results
The results of the analytical tests of the nano metal rod polymers prepared by the above methods according to the methods of examples 1 to 3 show that the nano platinum rod polymer composite materials prepared by the method also have the self-repairing and polarization patterning properties described above.
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention, and not to limit the scope of the present invention, and that other variations and modifications based on the above description and thought may be made by those skilled in the art, and that all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A preparation method of a self-repairing composite material with polarization patterning capability is characterized by comprising the following steps:
s1: dissolving a polymer monomer A and a polymer monomer B in a solvent, uniformly mixing, adding an initiator, and carrying out polymerization reaction under an oxygen-free condition to obtain a copolymer;
s2: adding the nano metal into the copolymer obtained in the step S1, heating and uniformly mixing to obtain a nano metal polymer;
s3: will contain Fe3+Dissolving the inorganic salt in polybasic acid, adjusting the pH value to 2-5, adding the inorganic salt into the nano metal polymer obtained in the step S2, heating and uniformly mixing to obtain a self-repairing composite material with polarization patterning capability;
the polymer monomer A is one or more of acrylic acid, acrylic acid derivatives, methyl acrylate derivatives, methacrylic acid derivatives, methyl methacrylate and methyl methacrylate derivatives;
the polymer monomer B is 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate.
2. The preparation method according to claim 1, wherein the solvent is one or more of water, methanol and ethanol; the initiator is one or two of 2-20% of ammonium persulfate and 2-20% of potassium persulfate; the nano metal is one or more of gold nanorods, silver nanorods and platinum nanorodsSeed growing; said Fe-containing3+The inorganic salt is one or more of ferric chloride, ferric sulfate and ferric nitrate; the polybasic acid is one or more of citric acid, tartaric acid and oxalic acid.
3. The method according to claim 1, wherein the polymer monomer A, the polymer monomer B, the solvent, the initiator, the nano-metal, and the Fe-containing compound are mixed to prepare the polymer3+The inorganic salt and the polybasic acid have the following weight part ratio: 5-50: 5-50: 0-90: 0.1-3: 0.1-1: 0.01-5: 0.01 to 5.
4. The method according to claim 3, wherein the polymer monomer A, the polymer monomer B, the solvent, the initiator, the nano-metal, and the Fe-containing compound are mixed to prepare the polymer3+The inorganic salt and the polybasic acid have the following weight part ratio: 8.5-21.5: 8.5-21.5: 70-80: 0.1-3: 0.3-0.5: 0.05-0.1: 0.25 to 0.5.
5. The method according to claim 4, wherein the polymer monomer A, the polymer monomer B, the solvent, the initiator, the nano-metal, and the Fe-containing compound are mixed to prepare the polymer3+The inorganic salt and the polybasic acid have the following weight part ratio: 8.5: 21.5: 70: 0.3: 0.3: 0.05: 0.25.
6. the preparation method according to claim 2, wherein the length-diameter ratio of the gold nanorods, the silver nanorods and the platinum nanorods is 2-4.7.
7. The method of claim 1, wherein the oxygen-free condition in step S1 is introducing nitrogen gas into the system.
8. The method according to claim 7, wherein the polymerization temperature in step S1 is 65-75 ℃ and the polymerization time is 6-12 h.
9. The method of claim 8, wherein the heating and mixing in steps S2 and S3 are performed at a temperature of 60-100 ℃.
10. The self-repairing composite material with polarization patterning capability prepared by the method of any one of claims 1 to 9.
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