CN111019327B - Polymer composite material with mechanochromism and self-repairing functions and preparation method thereof - Google Patents

Polymer composite material with mechanochromism and self-repairing functions and preparation method thereof Download PDF

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CN111019327B
CN111019327B CN201911326026.4A CN201911326026A CN111019327B CN 111019327 B CN111019327 B CN 111019327B CN 201911326026 A CN201911326026 A CN 201911326026A CN 111019327 B CN111019327 B CN 111019327B
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self
repairing
polymer
fluorescent
ultraviolet shielding
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CN111019327A (en
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李国良
宋晓珂
齐涛
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Institute of Process Engineering of CAS
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/422—Luminescent, fluorescent, phosphorescent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/762—Self-repairing, self-healing
    • 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
    • C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Abstract

The invention relates to a high polymer composite material with double functions of force-induced color change and self-repair. The polymer composite material has a double-layer structure, wherein the double-layer structure comprises a fluorescent self-repairing polymer matrix layer and an ultraviolet shielding layer; the thickness of the fluorescent self-repairing polymer matrix layer is at least 10 micrometers, and the thickness of the ultraviolet shielding layer is 0.1-8 micrometers; the fluorescent self-repairing polymer matrix layer consists of a self-repairing polymer matrix and a fluorescent additive, wherein the fluorescent additive accounts for 0.001-50% of the weight percentage; the ultraviolet shielding layer is composed of fragile polymers and an ultraviolet shielding agent, and the proportion of the ultraviolet shielding agent is 1-99% by weight. The polymer composite material shows a force-induced color change effect of gradually enhanced fluorescence intensity along with strain increase, and can realize repeated self-repairing at the same position by heating when being damaged, and recover the mechanical property and the force-induced color change property.

Description

Polymer composite material with mechanochromism and self-repairing functions and preparation method thereof
Technical Field
The invention belongs to the field of composite material preparation, and mainly relates to a high polymer composite material with force-induced color change and self-repairing functions and a preparation method thereof.
Background
In complex environments, ubiquitous mechanical forces tend to cause irreversible damage to materials. The development of multifunctional self-adaptive materials with mechanical force responsiveness is of great significance. In recent years, the mechanochromic material capable of changing optical properties under mechanical stimulation has attracted attention, and the performance of the mechanochromic material enables the mechanochromic material to have wide potential application values in the fields of damage monitoring, information encryption, flexible display and the like. The self-repairing material has the characteristics of automatically repairing the damaged part, and recovering the structural integrity and the mechanical property of the material. The mechanochromic function and the self-repairing function are integrated into a system, and the development of the polymer composite material with the mechanochromic and self-repairing functions has great significance for enhancing the adaptivity of the material, prolonging the service life of the material and saving energy.
Most of the electrochromic materials have been constructed by chemically bonding a mechanochromosome having a mechanical force responsiveness to a polymer skeleton, and thus the synthesis method is complicated and the mechanochromism sensitivity is low. In contrast, the force-induced color-changing polymer composite material constructed by a special structural design has the advantages of simple preparation, obvious color change before and after stress and the like. Songshan Zeng et al constructed a composite material (Nature Communications,2016,7,11802) with high mechanochromic sensitivity by utilizing strain-induced cracking and folding, but the material prepared by the method still has single performance, can nearly realize the indication of mechanical force, and cannot repair mechanical damage. Recently, a series of super-toughness self-repairing polymers (CN109982193A) are synthesized by Yan Song and the like by utilizing the interaction of multi-level hydrogen bonds, and the self-repairing polymers contain a large number of one-hydrogen bonds, two-hydrogen bonds and four-hydrogen bonds, so that the material can realize better self-repairing at lower temperature. However, the self-repairing polymer does not have a mechanical force monitoring function, and cannot realize sensing of mechanical force and early warning of early damage. Therefore, there is a great need to develop a polymer composite material having both mechanochromism and self-repairing functions.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel macromolecular composite material with double functions of force-induced discoloration and self-repair and a preparation method thereof.
The principle of the invention is as follows: the fluorescence additive is used as a fluorescent substance, and under ultraviolet light, the size of the fluorescence exposure area is adjusted through the expansion and closing of cracks on the ultraviolet shielding layer under different strains, so that the change of fluorescence intensity and mechanical force is realized. In addition, when the material is damaged, the self-repairing of the material can be realized through the interaction of supermolecules in the fluorescent self-repairing layer.
The polymer composite material with the force-induced color change and self-repair functions has a double-layer structure, wherein the double-layer structure comprises a fluorescent self-repair polymer layer and an ultraviolet shielding layer, and the fluorescent self-repair polymer matrix layer is positioned below the ultraviolet shielding layer.
Preferably, the thickness of the fluorescent self-repairing polymer matrix layer is at least 10 μm; the thickness of the ultraviolet shielding layer is 0.1-8 mu m.
Further preferably, the thickness of the fluorescent self-repairing polymer matrix layer is 300-500 μm; the thickness of the ultraviolet shielding layer is 1-4 mu m.
Preferably, the fluorescent self-repairing polymer matrix layer consists of a self-repairing polymer and a fluorescent additive, wherein the fluorescent additive accounts for 0.001-50 wt% of the fluorescent self-repairing polymer layer, and is further preferably 0.05-0.5 wt%; the ultraviolet shielding layer is composed of fragile polymers and an ultraviolet shielding agent, and the proportion of the ultraviolet shielding agent accounts for 1-99% of the weight percentage of the ultraviolet shielding layer, and is preferably 40-80%.
Preferably, the self-repairing polymer is a polymer elastomer with supramolecular interaction, and the supramolecular interaction comprises one or more of hydrogen bond interaction, metal-ligand interaction and host-guest interaction.
Preferably, the self-repairing polymer is one or more than two of polyurethane, polystyrene, polyolefin and polyamide.
Preferably, the fluorescent additive comprises one or more of rhodamine-B, rhodamine-6G, tetraethylrhodamine, tetramethyl rhodamine isothiocyanate, fluorescein, 9, 10-bis (4-methoxyphenyl) -2-chloroanthracene, fluorescein isothiocyanate, phycoerythrin and lanthanide chelate.
Preferably, the brittle polymer includes one or more of polyvinyl alcohol, polyvinyl chloride, polystyrene, polypropylene, polyethylene, polyester, and nylon.
Preferably, the ultraviolet screening agent includes one or more of titanium dioxide, zinc oxide, kaolin, talc and iron oxide.
The fluorescent self-repairing polymer layer and the ultraviolet shielding layer are prepared step by step and then are heated and compounded to obtain the fluorescent self-repairing polymer film with the obvious double-layer structure. The ultraviolet shielding layer can effectively shield ultraviolet rays and control the display and extinction of fluorescence, and the lower layer contains supermolecule interaction and gives the material a self-repairing function.
In the method and the implementation example provided by the invention, the control of the material force-induced discoloration performance is realized mainly by controlling the content of the ultraviolet screening agent in the ultraviolet screening layer and the thickness of the ultraviolet screening layer.
The invention provides a preparation method of a high polymer composite material with force-induced discoloration and self-repair functions, which comprises the following steps:
step S-1: uniformly mixing the self-repairing polymer with the fluorescent additive to form a film A;
step S-2: uniformly mixing the brittle polymer and the ultraviolet screening agent, and spraying the mixture on a substrate to form a film B;
step S-3: placing the film A on the film B, heating and compounding the film A, and then taking off the film A from the substrate to obtain the macromolecular composite material with the photochromic and self-repairing functions, wherein the heating time is at least 0.1h, and the heating temperature is at least 20 ℃;
corresponding to the operation steps of the invention, the invention also has the following characteristics:
the self-repairing polymer in the step S-1 contains supermolecular interaction, including one or more of hydrogen bond interaction, ionic bond interaction, metal-ligand interaction and host-guest interaction;
the self-repairing polymer in the step S-1 is one or more of polyurethane, polystyrene, polyolefin and polyamide;
the proportion of the fluorescent additive in the step S-1 accounts for 0.001-50 wt% of the fluorescent self-repairing polymer layer, and preferably 0.05-0.5 wt%;
the proportion of the ultraviolet screening agent in the step S-2 accounts for 1-99% of the weight of the ultraviolet shielding layer, and preferably 40-80%;
the ultraviolet screening agent in the step S-2 is one or more of titanium dioxide, zinc oxide, kaolin, talcum powder and ferric oxide;
the step S-2; the brittle polymer comprises one or more of polyvinyl alcohol, polyvinyl chloride, polystyrene, polypropylene, polyethylene, polyester and nylon;
in the step S-3, the heating time is at least 0.1h, and the heating temperature is at least 20 ℃; the preferable heating time is 6-24 h, and the preferable heating temperature is 55-70 ℃;
according to the technical points, the polymer composite material with photochromic and self-repairing functions can be prepared, and the polymer composite material has a double-layer structure and comprises a fluorescent self-repairing polymer layer and an ultraviolet shielding layer, wherein the thickness of the fluorescent self-repairing polymer layer is at least 10 micrometers, and the thickness of the ultraviolet shielding layer is 0.1-8 micrometers.
The invention has the following beneficial results:
the material provided by the invention is a novel high-molecular composite material which has the double functions of force-induced discoloration and self-repairing and contains a fluorescent self-repairing polymer layer and an ultraviolet shielding layer. The polymer composite material has almost no macroscopic fluorescence under ultraviolet light when not subjected to external force, but shows obvious fluorescence in a stretching state, thereby showing a force-induced discoloration effect. In addition, when the polymer composite material is damaged and broken, the damaged part can be repaired by low-temperature heating, and the integrity of the material is recovered. The repaired sample was nearly identical in mechanical properties to the original sample and was stretchable. Therefore, the polymer composite material can monitor mechanical stimulation and repair mechanical damage, can effectively enhance the material adaptability, prolong the material life, save resources, and has potential application in the fields of mechanical force sensing, information encryption and the like.
Drawings
FIG. 1 is a cross-sectional scanning electron microscope of the polymer composite of the present invention;
FIG. 2 is a photograph showing fluorescence after stretching, without fluorescence in the original state, under 254nm ultraviolet irradiation, according to the present invention;
FIG. 3 is a photograph showing the state after breakage under a fluorescent lamp, the state after repair, and the state after tension after repair according to the present invention.
Detailed Description
Example 1:
dissolving 4g of self-repairing polyurethane in 60mL of trichloromethane, adding 0.5mL of ethanol solution (0.01g/mL) of fluorescent additive rhodamine B, uniformly stirring, pouring the mixed solution into a polytetrafluoroethylene mold, volatilizing the solvent, and fully drying in a vacuum drying oven to obtain the membrane A. 0.1g of polyvinyl alcohol (molecular weight of 67000g/mol) is added into 10mL of deionized water, heated and stirred until the polyvinyl alcohol is completely dissolved, 0.4g of titanium dioxide nano-particles are added into the aqueous solution of the polyvinyl alcohol, and the mixture is stirred uniformly. 1.5mL of a mixture of polyvinyl alcohol and titanium dioxide nanoparticles was sprayed on the polystyrene base with a spray gun having a pen point of 0.3mm at a distance of about 20cm from the base, and dried overnight at room temperature to give film B. Cutting the membrane A into a proper size, placing on the membrane B, and standing at 55 ℃ for 24h for compounding. The film A, B is then peeled off from the substrate to obtain the polymer composite material with the functions of both force-induced color change and self-repair. The cross-sectional structure of the resulting polymer composite is shown in FIG. 1.
The relative fluorescence intensity of the sample of the embodiment shows obvious fluorescence enhancement along with the increase of the strain, as shown in fig. 2 and 3, when the strain reaches 100%, the fluorescence intensity can be increased by 13-15 times. In the embodiment, after the sample is disconnected, the sample is heated for 0.5 to 48 hours at the temperature of between 25 and 90 ℃, the repair efficiency can reach 20.2 to 98.3 percent, and the sample shows better self-repair performance. The sample can be stretched after self-repairing, and the change of the fluorescence intensity (excitation wavelength 254nm) of the sample at 597nm under different strains (0-100%) after the self-repairing is almost the same as that of the original sample, which indicates that the sample has the double functions of mechanochromism and self-repairing.
Example 2:
dissolving 4g of self-repairing polyurethane in 60mL of trichloromethane, adding 1mL of ethanol solution (0.01g/mL) of fluorescent additive fluorescein, uniformly stirring, pouring the mixed solution into a polytetrafluoroethylene mold, volatilizing the solvent, and fully drying in a vacuum drying oven to obtain the membrane A. 0.1g of polyvinyl alcohol (molecular weight of 67000g/mol) is added into 10mL of deionized water, heated and stirred until the polyvinyl alcohol is completely dissolved, 0.2g of titanium dioxide nano-particles are added into the aqueous solution of the polyvinyl alcohol, and the mixture is stirred uniformly. 1.5mL of a mixture of polyvinyl alcohol and titanium dioxide nanoparticles was sprayed on the polystyrene base with a spray gun having a pen point of 0.3mm at a distance of about 20cm from the base, and dried overnight at room temperature to give film B. Cutting the membrane A into a proper size, placing on the membrane B, and standing at 55 ℃ for 24h for compounding. The film A, B is then peeled off from the substrate to obtain the polymer composite material with the functions of both force-induced color change and self-repair.
Example 3:
dissolving 4g of self-repairing polyurethane in 60mL of trichloromethane, adding 1mL of ethanol solution (0.001g/mL) of rhodamine B as a fluorescent additive, uniformly stirring, pouring the mixed solution into a polytetrafluoroethylene mold, volatilizing the solvent, and fully drying in a vacuum drying oven to obtain the membrane A. 0.1g of polyvinyl alcohol (molecular weight of 67000g/mol) is added into 10mL of deionized water, heated and stirred until the polyvinyl alcohol is completely dissolved, 0.6g of titanium dioxide nano-particles are added into the aqueous solution of the polyvinyl alcohol, and the mixture is stirred uniformly. 1.5mL of a mixture of polyvinyl alcohol and titanium dioxide nanoparticles was sprayed on the polystyrene base with a spray gun having a pen point of 0.3mm at a distance of about 20cm from the base, and dried overnight at room temperature to give film B. Cutting the membrane A into a proper size, placing on the membrane B, and standing at 55 ℃ for 24h for compounding. The film A, B is then peeled off from the substrate to obtain the polymer composite material with the functions of both force-induced color change and self-repair.
Example 4:
dissolving 4g of self-repairing polyurethane in 60mL of trichloromethane, adding 1mL of trichloromethane solution (0.001g/mL) of a fluorescent additive 9, 10-bis (4-methoxyphenyl) -2-chloroanthracene, uniformly stirring, pouring the mixed solution into a polytetrafluoroethylene mold to volatilize the solvent, and fully drying in a vacuum drying oven to obtain the membrane A. 0.1g of polyvinyl alcohol (molecular weight of 67000g/mol) is added into 10mL of deionized water, heated and stirred until the polyvinyl alcohol is completely dissolved, 0.4g of titanium dioxide nano-particles are added into the aqueous solution of the polyvinyl alcohol, and the mixture is stirred uniformly. 1.5mL of a mixture of polyvinyl alcohol and titanium dioxide nanoparticles was sprayed on the polystyrene base with a spray gun having a pen point of 0.3mm at a distance of about 20cm from the base, and dried overnight at room temperature to give film B. Cutting the membrane A into a proper size, placing on the membrane B, and standing at 55 ℃ for 24h for compounding. The film A, B is then peeled off from the substrate to obtain the polymer composite material with the functions of both force-induced color change and self-repair.
Example 5:
dissolving 4g of self-repairing polyurethane in 60mL of trichloromethane, adding 1mL of ethanol solution (0.001g/mL) of fluorescein serving as a fluorescent additive, uniformly stirring, pouring the mixed solution into a polytetrafluoroethylene mold, volatilizing the solvent, and fully drying in a vacuum drying oven to obtain the membrane A. 0.1g of polyvinyl alcohol (molecular weight of 67000g/mol) is added into 10mL of deionized water, heated and stirred until the polyvinyl alcohol is completely dissolved, 0.4g of titanium dioxide nano-particles are added into the aqueous solution of the polyvinyl alcohol, and the mixture is stirred uniformly. 1.5mL of a mixture of polyvinyl alcohol and titanium dioxide nanoparticles was sprayed on the polystyrene base with a spray gun having a pen point of 0.3mm at a distance of about 20cm from the base, and dried overnight at room temperature to give film B. Cutting the membrane A into a proper size, placing on the membrane B, and standing at 55 ℃ for 24h for compounding. The film A, B is then peeled off from the substrate to obtain the polymer composite material with the functions of both force-induced color change and self-repair.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (6)

1. A polymer composite material with the double functions of mechanochromism and self-repairing is characterized in that the polymer composite material has a double-layer structure; the double-layer structure comprises a fluorescent self-repairing polymer matrix layer and an ultraviolet shielding layer, wherein the fluorescent self-repairing polymer matrix layer is positioned below the ultraviolet shielding layer;
the fluorescent self-repairing polymer matrix layer consists of a self-repairing polymer and a fluorescent additive, and the proportion of the fluorescent additive accounts for 0.001-50% of the weight percentage of the fluorescent self-repairing polymer layer;
the ultraviolet shielding layer is composed of fragile polymers and an ultraviolet shielding agent, and the proportion of the ultraviolet shielding agent accounts for 1-99% of the weight percentage of the ultraviolet shielding layer;
the fragile polymer comprises one or more than two of polyvinyl alcohol, polyvinyl chloride, polystyrene, polypropylene, polyethylene, polyester and nylon;
the fluorescent self-repairing polymer is a polymer elastomer with supramolecular interaction, and the supramolecular interaction comprises one or more of hydrogen bond interaction, metal-ligand interaction and host-guest interaction.
2. The polymeric composite of claim 1, wherein the fluorescent self-healing polymer matrix layer has a thickness of at least 10 μ ι η; the thickness of the ultraviolet shielding layer is 0.1-8 mu m.
3. The polymer composite material of claim 1, wherein the fluorescent self-healing polymer is one or more of polyurethane, polystyrene, polyolefin, and polyamide.
4. The polymer composite according to claim 1, wherein the fluorescent additive comprises one or more of rhodamine-B, rhodamine-6G, tetraethylrhodamine, tetramethylrhodamine isothiocyanate, fluorescein, 9, 10-bis (4-methoxyphenyl) -2-chloroanthracene, phycoerythrin, and lanthanide chelate.
5. The polymer composite material according to claim 1, wherein the ultraviolet shielding agent comprises one or more of titanium dioxide, zinc oxide, kaolin, talc and iron oxide.
6. A method for preparing the polymer composite material with the functions of force-induced discoloration and self-repair as claimed in any one of claims 1 to 5, comprising the following steps:
step S-1: uniformly mixing the self-repairing polymer with the fluorescent additive to form a film A;
step S-2: uniformly mixing the brittle polymer and the ultraviolet screening agent, and spraying the mixture on a substrate to form a film B;
step S-3: and placing the film A on the film B, heating and compounding the film A, and then taking off the film A from the substrate to obtain the macromolecular composite material with the photochromic and self-repairing functions, wherein the heating time is at least 0.1h, and the heating temperature is at least 20 ℃.
CN201911326026.4A 2019-12-20 2019-12-20 Polymer composite material with mechanochromism and self-repairing functions and preparation method thereof Active CN111019327B (en)

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