CN113321924A - Composite material with photo-thermal self-healing function and preparation method thereof - Google Patents
Composite material with photo-thermal self-healing function and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of high polymer materials and functional coatings, and provides a composite material with a photo-thermal self-healing function and a preparation method thereof. The preparation method is efficient and convenient, and the introduced dynamic diselenide bond enables the polyurethane matrix to be broken and rearranged under the condition of thermal stimulation, thereby realizing the self-healing capability of the material. Meanwhile, the modified graphene oxide has excellent photo-thermal characteristics, and is dispersed in a polyurethane matrix in a chemical combination mode, so that the material can convert light energy into heat energy when being irradiated by remote infrared laser, and self-healing of the material is realized. The material has wide application prospect in the fields of aerospace, automobile industry and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials and functional coatings, and particularly relates to a composite material with a photo-thermal self-healing function and a preparation method thereof.
Background
In the actual use process of the high polymer material, the service life of the material is often greatly reduced due to the existence of mechanical fatigue, abrasion and the like, so that higher requirements on the service life of the material are provided in the fields of aviation, automobile industry and the like. The self-healing material can well utilize the self characteristics, can recover the self defects to a certain extent and achieves the purpose of prolonging the service life. However, in the previous research, the self-healing process of the polymer material based on the dynamic covalent bond is often realized by external stimulation such as heating and adding a catalyst, and the characteristics such as remote, precise control and rapid healing cannot be achieved. Therefore, the design of a functional material which can start a healing mechanism of the material by utilizing remote illumination has wide application prospect.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to introduce a diselenium covalent bond having excellent dynamic responsiveness into a polyurethane system to ensure a self-healing function of a polyurethane molecular chain, chemically modify graphene oxide using diisocyanate, and blend the modified graphene oxide with polyurethane to obtain a composite material. By utilizing the excellent photo-thermal conversion characteristic of graphene oxide, the self-healing function of remote control by infrared laser is realized, and the composite material with the photo-thermal self-healing function is obtained.
The invention provides a preparation method of a composite material with a photo-thermal self-healing function, which is characterized by comprising the following steps: step 1, dispersing graphene oxide in a DMF (dimethyl formamide) solution in an inert gas atmosphere, adding diisocyanate, stirring and reacting at room temperature to obtain a reaction solution, pouring the reaction solution into dichloromethane to obtain a turbid solution, and performing centrifugal separation on the turbid solution to obtain modified graphene oxide; step 2, adding selenium powder into an aqueous solution of sodium borohydride in an ice bath environment, mixing and stirring, heating to 70-80 ℃, and heating to obtain an aqueous solution of sodium selenide; step 3, adding a sodium selenide aqueous solution into the 11-bromo-1-undecanol solution under an inert gas atmosphere, heating to 40-60 ℃ for reaction to obtain a light yellow solid, and purifying the light yellow solid to obtain yellow powder, namely a hydroxyl-terminated diselenide bond monomer; step 4, slowly adding a diisocyanate solution into a dihydric alcohol solution in an inert gas atmosphere, heating and reacting for a period of time, then dropwise adding a hydroxyl-terminated diselenide bond monomer, and continuing to react to obtain a polyurethane system; and 5, dissolving the modified graphene oxide in the step 1 in a DMF (dimethyl formamide) solution in an inert gas atmosphere, adding the solution into the polyurethane system obtained in the step 4, heating and stirring the solution, then carrying out ultrasonic treatment, finally transferring the mixed solution into a mold, and heating the mixed solution to obtain a target product, namely the composite material with the photo-thermal self-healing function.
The preparation method of the composite material with the photo-thermal self-healing function provided by the invention can also have the following characteristics: wherein the molar ratio of the dihydric alcohol to the diisocyanate is 1.0-1.2, and the molar ratio of the hydroxyl-terminated diselenide bond monomer to the dihydric alcohol is 0.8-1.0.
The preparation method of the composite material with the photo-thermal self-healing function provided by the invention can also have the following characteristics: wherein the dihydric alcohol is any one of dihydroxy terminated polycaprolactone with Mn of 2000-4000, polytetramethylene ether glycol with Mn of 2000-4000 or polypropylene glycol with Mn of 2000-4000, and the diisocyanate is diphenylmethane diisocyanate or isophorone diisocyanate.
The preparation method of the composite material with the photo-thermal self-healing function provided by the invention can also have the following characteristics: in the step 1, the mass ratio of the graphene oxide to the diisocyanate is 0.1-0.4.
The preparation method of the composite material with the photo-thermal self-healing function provided by the invention can also have the following characteristics: wherein, in the step 5, the mass of the modified graphene oxide is 0.3-1.5% of the total mass of the diisocyanate, the dihydric alcohol and the hydroxyl-terminated diselenide bond monomer in the step 4.
The preparation method of the composite material with the photo-thermal self-healing function provided by the invention can also have the following characteristics: wherein, in the step 3, the purification operation of the light yellow solid is as follows: adding dichloromethane in a volume ratio of 4: 1: ethyl acetate is used as eluent, and after purification by a chromatographic column, the ethyl acetate is subjected to rotary evaporation to obtain yellow powder, namely the hydroxyl-terminated diselenide bond monomer.
The preparation method of the composite material with the photo-thermal self-healing function provided by the invention can also have the following characteristics: wherein, in the step 4, dibutyltin dilaurate is added as a catalyst.
The invention also provides a composite material with the photo-thermal self-healing function, which is characterized by being prepared by the preparation method of the composite material with the photo-thermal self-healing function.
Action and Effect of the invention
According to the composite material with the photo-thermal self-healing function and the preparation method thereof, a hydroxyl-terminated diselenide bond monomer containing a dynamic diselenide bond is synthesized, and then the hydroxyl-terminated diselenide bond monomer is added into a system of diisocyanate solution and dihydric alcohol to obtain a polyurethane system. In the polyurethane system, a hydroxyl-terminated diselenide bond monomer is used as a chain extender to carry out chain extension on a polyurethane prepolymer synthesized by diisocyanate and dihydric alcohol, and the diisocyanate and the dihydric alcohol are main bodies of polyurethane chain segments.
The graphene oxide modified by diisocyanate is added into a polyurethane system to obtain a blending system consisting of polyurethane and graphene oxide, wherein the graphene oxide has a monoatomic layer structure and a large specific surface area, and a large number of modifiable oxygen-containing functional groups exist on two base planes, so that the graphene oxide and the diisocyanate undergo chemical reaction by utilizing the characteristics of the graphene oxide, the graphene oxide and hydroxyl at the tail end of a linear polyurethane molecule can further undergo chemical crosslinking, the binding force between a polyurethane matrix and the graphene oxide is improved, and the mechanical properties of the material are improved. On the other hand, graphene oxide is mainly hybridized by sp3 and sp2, can absorb near-infrared light energy through energy level transition and convert the near-infrared light energy into heat energy, is an excellent photo-thermal conversion material, and can fully heat the material when being irradiated by infrared laser by dispersing the near-infrared light energy into the polyurethane matrix to trigger the dynamic chemical process of diselenide bonds, so that self-healing is realized.
In a polyurethane system, the diselenide bond chain extender can introduce a dynamic covalent bond into a linear molecular structure of polyurethane, and the diselenide bond belongs to one type of dynamic reversible covalent bond, can realize reversible covalent bond fracture and reconstruction under proper external stimulus, and has weaker covalent bond energy compared with the study of wider disulfide bonds, Diels-Alder bonds and the like, and can stimulate the dynamic fracture under the milder external stimulus condition, so that the diselenide bond-based polyurethane matrix has the self-healing capacity under the thermal stimulus condition, and a premise is provided for realizing the functions of the photo-thermal self-healing composite material.
The preparation method realizes the self-healing capacity of the polyurethane matrix under the condition of thermal stimulation by introducing the dynamic diselenide bond; in addition, the graphene oxide modified by diisocyanate can be combined with hydroxyl at the tail end of a polyurethane molecular chain to form a more stable and uniform composite material structure, and the mechanical property of the composite material can be effectively improved due to good interface combination; the doping and blending operation of the polyurethane and the modified graphene oxide is simple and easy to implement, and samples with different physical and photo-thermal properties can be prepared by changing the proportion of doping components. The composite material with the photo-thermal self-healing function can effectively realize the remote, accurate, controllable and efficient self-healing capability, and the material has wide application prospect in the fields of aerospace, automobile coating and the like as a functional material.
Drawings
FIG. 1 is a diagram of the self-healing mechanism of the polyurethane matrix synthesized by the present invention;
fig. 2 is an XRD spectrum of modified graphene oxide in example 1 of the present invention;
FIG. 3 is an infrared spectrum of a polyurethane matrix in example 1 of the present invention;
FIG. 4 is an infrared spectrum of the polyurethane/modified graphene oxide of example 1 of the present invention at different reaction times;
fig. 5 is a sectional scanning electron microscope image of the polyurethane/modified graphene oxide composite material in example 1 of the present invention;
FIG. 6 is a scanning electron micrograph of a self-healing polyurethane matrix in example 1 of the present invention;
fig. 7 is an infrared thermal imaging diagram of the surface of the polyurethane/modified graphene oxide irradiated by an infrared laser in example 1 of the present invention; and
fig. 8 is a mechanical tensile curve diagram of the polyurethane/modified graphene oxide sample strip in example 1 of the present invention after irradiation with infrared laser.
Detailed Description
In order to make the technical means, creation features, achievement purposes and effects of the present invention easy to understand, the following embodiments and drawings are combined to specifically describe a composite material with a photo-thermal self-healing function and a preparation method thereof.
The raw materials used in the following examples were purchased from general commercial sources, and the specific models and manufacturer standards were as follows:
PCL, available from Tanshtech, purity grade 98%;
PTMEG, available from jaboticaba chemical ltd, purity grade 98%;
PPG, available from Acros, purity grade 98%;
MDI, available from Adamas, purity grade 95%;
IPDI, available from Adamas, purity grade 99%;
selenium powder, purchased from Alfa, purity grade 99%;
sodium borohydride, available from Adamas, purity grade 98%;
11-bromo-1-undecanol, available from Adamas, purity grade 98%;
graphene oxide, available from suzhou carbofeng graphene technologies ltd.
The synthetic route of the invention is as follows:
the invention provides a preparation method of a composite material with a photo-thermal self-healing function, which specifically comprises the following steps:
step 2, adding selenium powder into an aqueous solution of sodium borohydride in an ice bath environment, mixing and stirring, heating to 70-80 ℃, and heating to obtain an aqueous solution of sodium selenide;
step 3, adding a sodium selenide aqueous solution into the 11-bromo-1-undecanol solution under an inert gas atmosphere, heating to 40-60 ℃ for reaction to obtain a light yellow solid, and purifying the light yellow solid to obtain yellow powder, namely a hydroxyl-terminated diselenide bond monomer;
and 5, dissolving the modified graphene oxide obtained in the step 1 in a DMF (dimethyl formamide) solution in an inert gas atmosphere, adding the solution into a polyurethane solution, heating and stirring the solution, then carrying out ultrasonic treatment, finally transferring the mixed solution into a mold, and heating the mixed solution to obtain a target product, namely the composite material with the photo-thermal self-healing function.
Wherein the molar ratio of the dihydric alcohol to the diisocyanate is 1.0-1.2, and the molar ratio of the hydroxyl-terminated diselenide bond monomer to the dihydric alcohol is 0.8-1.0. The dihydric alcohol is one of dihydroxy terminated polycaprolactone with Mn of 2000-4000, polytetramethylene ether glycol with Mn of 2000-4000 or polypropylene glycol with Mn of 2000-4000, and the diisocyanate is diphenylmethane diisocyanate or isophorone diisocyanate.
In the step 1, the mass ratio of the graphene oxide to the diisocyanate is 0.1-0.4. In step 3, the purification operation of the light yellow solid is as follows: adding dichloromethane in a volume ratio of 4: 1: ethyl acetate is used as eluent, and after purification by a chromatographic column, the ethyl acetate is subjected to rotary evaporation to obtain yellow powder, namely the hydroxyl-terminated diselenide bond monomer. In the step 5, the mass of the modified graphene oxide is 0.3-1.5% of the total mass of the diisocyanate, the dihydric alcohol and the hydroxyl-terminated diselenide bond monomer in the step 4. The solution of polyurethane in step 5 may be obtained by dissolving polyurethane in a solvent, or may be a polyurethane system obtained by not drying in step 4. (it should be recognized that the claims are not supported herein because they are written differently in the claims than in the examples, unless so written.)
The prepared composite material with the photo-thermal self-healing function (hereinafter referred to as composite material) is a polyurethane/diisocyanate-modified graphene oxide composite material containing dynamic diselenide bonds, and the self-healing performance mechanism of the polyurethane matrix part is shown in fig. 1:
when the polyurethane matrix is scratched by external force, the dynamic chemical process of the diselenide covalent bond is excited by raising the temperature, so that the polyurethane linear molecules are broken into a plurality of small chain segments, and the polyurethane linear molecules are moved and rephotographed under the synergistic action of thermal motion and intermolecular hydrogen bonds to close cracks. When the temperature of the material is reduced, the dynamic covalent bond is coupled into a new diselenide bond again, and then the self-healing function is achieved.
< example 1>
Weighing 1g of dried graphene oxide in a round-bottom flask, adding 60ml of DMF solvent, and ultrasonically oscillating for 30 min. The system was then flushed with nitrogen and a solution of diphenylmethane diisocyanate (10.01g, 40mmol) in DMF was injected into the system and the reaction stirred at room temperature for 24 h. Then pouring the liquid into 600ml dichloromethane for standing, transferring to a centrifuge for 5min by 3600r/min, removing supernatant, adding dichloromethane to wash lower-layer sediments, repeating the centrifugation-washing operation for 3 times, taking out the final centrifugal sediments, and obtaining a final product after suction filtration and vacuum drying: and (3) modifying the graphene oxide.
Dissolving sodium borohydride (1.71g, 45mmol) in 15ml of deionized water, adding selenium powder (3.57g, 45mmol) in an ice bath, fully stirring, heating to 80 ℃, and continuously heating for 5 hours to obtain the sodium selenide aqueous solution. Another 11-bromo-1-undecanol was dissolved in THF, and 15ml of the obtained aqueous sodium selenide solution was injected under the same atmosphere, and the temperature was raised to 50 ℃ and stirred for 24 hours. And finally, purifying by a chromatographic column and then carrying out rotary evaporation to obtain a yellow powder product, namely the micromolecule chain extender (namely the hydroxyl-terminated diselenide bond monomer) containing diselenide bonds.
The dried bishydroxy-terminated Polycaprolactone (PCL) (5g, 2.5mmol) was mixed with diphenylmethane diisocyanate (MDI) (1.25g, 5mmol) under nitrogen and a drop of dibutyltin dilaurate (DBTDL) (2.5mg, 0.004mmol) was added dropwise as catalyst. Heating to 80 ℃ and stirring for 4h to obtain the polyurethane prepolymer solution. And then adding 1.28g of the prepared diselenide bond chain extender into the system, fully stirring, transferring the mixture into a mold, and drying the mixture in an oven at the temperature of 80 ℃ for 24 hours to obtain a polyurethane product.
Finally, 0.11g of modified graphene oxide powder is dissolved in DMF, and the solution is fully ultrasonically dispersed for later use. And dissolving another 10g of polyurethane product in DMF, blending the polyurethane product with the solution of the modified graphene oxide in a nitrogen atmosphere, fully stirring the mixture, and transferring the mixture to an oven at 80 ℃ for heating for 12 hours to obtain the final composite material.
< example 2>
Weighing 1g of dried graphene oxide in a round-bottom flask, adding 60ml of DMF solvent, and ultrasonically oscillating for 30 min. The system was then flushed with nitrogen and a solution of diphenylmethane diisocyanate (10.01g, 40mmol) in DMF was injected into the system and the reaction stirred at room temperature for 24 h. Then pouring the liquid into 600ml dichloromethane for standing, transferring to a centrifuge for 5min by 3600r/min, removing supernatant, adding dichloromethane to wash lower-layer sediments, repeating the centrifugation-washing operation for 3 times, taking out the final centrifugal sediments, and obtaining a final product after suction filtration and vacuum drying: and (3) modifying the graphene oxide.
Dissolving sodium borohydride (1.71g, 45mmol) in 15ml of deionized water, adding selenium powder (3.57g, 45mmol) in an ice bath, fully stirring, heating to 80 ℃, and continuously heating for 5 hours to obtain the sodium selenide aqueous solution. Another 11-bromo-1-undecanol was dissolved in THF, and 15ml of the obtained aqueous sodium selenide solution was injected under the same atmosphere, and the temperature was raised to 50 ℃ and stirred for 24 hours. And finally, purifying by a chromatographic column and then carrying out rotary evaporation to obtain a yellow powder product, namely the micromolecule chain extender containing diselenide bonds.
The dried bishydroxy-terminated Polycaprolactone (PCL) (5g, 2.5mmol) was mixed with diphenylmethane diisocyanate (MDI) (1.25g, 5mmol) under nitrogen and a drop of dibutyltin dilaurate (DBTDL) (2.5mg, 0.004mmol) was added dropwise as catalyst. Heating to 70 ℃ and stirring for 5h to obtain the polyurethane prepolymer solution. And then adding 1.28g of the prepared diselenide bond chain extender into the system, fully stirring, transferring the mixture into a mold, and drying the mixture in an oven at the temperature of 80 ℃ for 24 hours to obtain a polyurethane product.
Finally, 0.09g of modified graphene oxide powder is dissolved in DMF and is fully ultrasonically dispersed for later use. And dissolving another 10g of polyurethane product in DMF, blending the polyurethane product with the solution of the modified graphene oxide in a nitrogen atmosphere, fully stirring the mixture, and transferring the mixture to an oven at 80 ℃ for heating for 12 hours to obtain the final composite material.
< example 3>
Weighing 1g of dried graphene oxide in a round-bottom flask, adding 60ml of DMF solvent, and ultrasonically oscillating for 30 min. The system was then flushed with nitrogen and a solution of diphenylmethane diisocyanate (10.01g, 40mmol) in DMF was injected into the system and the reaction stirred at room temperature for 24 h. Then pouring the liquid into 600ml dichloromethane for standing, transferring to a centrifuge for 5min by 3600r/min, removing supernatant, adding dichloromethane to wash lower-layer sediments, repeating the centrifugation-washing operation for 3 times, taking out the final centrifugal sediments, and obtaining a final product after suction filtration and vacuum drying: and (3) modifying the graphene oxide.
Dissolving sodium borohydride (1.71g, 45mmol) in 15ml of deionized water, adding selenium powder (3.57g, 45mmol) in an ice bath, fully stirring, heating to 80 ℃, and continuously heating for 5 hours to obtain the sodium selenide aqueous solution. Another 11-bromo-1-undecanol was dissolved in THF, and 15ml of the obtained aqueous sodium selenide solution was injected under the same atmosphere, and the temperature was raised to 50 ℃ and stirred for 24 hours. And finally, purifying by a chromatographic column and then carrying out rotary evaporation to obtain a yellow powder product, namely the micromolecule chain extender containing diselenide bonds.
The dried bishydroxy-terminated Polycaprolactone (PCL) (5g, 2.5mmol) was mixed with diphenylmethane diisocyanate (MDI) (1.25g, 5mmol) under nitrogen and a drop of dibutyltin dilaurate (DBTDL) (2.5mg, 0.004mmol) was added dropwise as catalyst. Heating to 80 ℃ and stirring for 3h to obtain the polyurethane prepolymer solution. And then adding 1.28g of the prepared diselenide bond chain extender into the system, fully stirring, transferring the mixture into a mold, and drying the mixture in an oven at the temperature of 80 ℃ for 24 hours to obtain a polyurethane product.
Finally, 0.07g of modified graphene oxide powder is dissolved in DMF, and the solution is fully ultrasonically dispersed for later use. And dissolving another 10g of polyurethane product in DMF, blending the polyurethane product with the solution of the modified graphene oxide in a nitrogen atmosphere, fully stirring the mixture, and transferring the mixture to an oven at 80 ℃ for heating for 12 hours to obtain the final composite material.
< test example >
1. XRD characterization of the modified graphene oxide:
in order to verify the chemical modification of diphenylmethane diisocyanate and graphene oxide and to explore the change of the modified structure, an X-ray powder polycrystalline diffractometer was used to perform X-ray diffraction analysis on the initial graphene oxide and the modified graphene oxide in example 1, and the test results are shown in fig. 2.
Fig. 2 is an ultraviolet absorption spectrum of modified graphene oxide in example 1 of the present invention.
As shown in fig. 2, the bead peak of the original graphene oxide is located at 11.9 ° 2 θ, the interlayer distance of the graphene oxide is calculated to be 0.74nm according to the bragg equation, and the main peak characteristic peaks of the modified graphene oxide are shifted to 6.76 ° 2 θ and 21.16 ° 2 θ. The generation of the new peak is because the molecular volume of the diisocyanate is larger, and the contained benzene ring forms a new characteristic peak on the basis of the original structure of the graphene oxide, so that the combination of the diphenylmethane diisocyanate and the graphene oxide is not simple physical adsorption, but is chemically modified in a chemical grafting mode.
2. Infrared spectrogram of polyurethane matrix and composite material:
to verify that the synthesized polyurethane meets the experimental expectations, the surface of the sample synthesized in example 1 was characterized by an infrared spectrum, and the results are shown in fig. 3.
FIG. 3 is an infrared spectrum of a polyurethane matrix in example 1 of the present invention.
As shown in FIG. 3, the characteristic absorption peak of the isocyanate at 2000-2300cm-1 is completely disappeared, thus proving that the isocyanate completely participates in the reaction; the afflictions appearing at 3420 and 1533 are ascribed to characteristic absorption peaks of the imino group on the urethane bond formed by the reaction, and thus the product can be judged as a polyurethane structure.
In order to verify that the chemical doping of the synthesized polyurethane and the modified graphene oxide meets the experimental expectation, in example 1, infrared spectrograms of samples with different reaction times are performed after the modified graphene oxide and the polyurethane solution are blended, and the result is shown in fig. 4, wherein three curves from top to bottom are the infrared spectrograms of the composite material obtained under the conditions of 4 hours, 8 hours and 12 hours of blending reaction respectively.
Fig. 4 is an infrared spectrum of the polyurethane/modified graphene oxide in example 1 of the present invention at different reaction times.
As shown in FIG. 4, the characteristic absorption peak of the isocyanate at 2268cm-1 is weakened with the prolonging of the drying time and finally disappears completely after 12h, which proves that the isocyanate on the surface of the modified graphene oxide completely participates in the reaction, and simultaneously shows that the polyurethane and the graphene oxide are connected by means of chemical bonds rather than simple physical blending.
3. Scanning electron microscope test
In order to more intuitively observe the distribution state of the modified graphene oxide in the polyurethane matrix, the prepared composite material is observed by a scanning electron microscope with a section, and the observation result is shown in fig. 5.
Fig. 5 is a sectional scanning electron microscope image of the polyurethane/modified graphene oxide composite material in example 1 of the present invention.
As shown in fig. 5, no agglomerates of the modified graphene oxide were observed in the cut surface of the composite material, indicating that the modified graphene oxide had good dispersibility in the polyurethane matrix.
4. Self-healing performance testing of polyurethane matrices
The self-healing capability of the polyurethane matrix under the condition of thermal driving is the basis for realizing photo-thermal self-healing of the composite material, in order to verify the self-healing capability of the polyurethane matrix, the composite material prepared in example 1 is subjected to heat treatment after surface scratching, the self-healing appearance after the heat treatment is observed, the test result is observed through a scanning electron microscope, and the result is shown in fig. 6, wherein (a) is the surface appearance of a sample after surface scratching, and (b) is the surface appearance after heat treatment at 80 ℃ for 3 hours.
Fig. 6 is a self-healing scanning electron micrograph of a polyurethane matrix in example 1 of the present invention.
As shown in fig. 6, when the scratched sample was heated at 80 ℃ for 3 hours, the scratch mark on the surface almost completely disappeared, and only a slight mark after healing remained, and in addition, the distortion and orientation caused by the cut wound around the initial scratch completely disappeared with the heat treatment. The self-healing degree of the polyurethane matrix is higher, the performance of the material can be effectively recovered, and a foundation is laid for realizing the photo-thermal self-healing function.
5. Testing of photo-thermal self-healing performance of composite material
The excellent photothermal conversion performance of graphene oxide is the basis for realizing the photothermal characteristics of the composite material, and in order to explore the photothermal conversion capability of the composite material, the temperature rise of the surface of the composite material prepared in examples 1, 2 and 3 under continuous infrared laser irradiation is recorded by using an infrared thermal imaging camera, and the test result is shown in fig. 7.
Fig. 7 is an infrared thermal imaging diagram of the surface of the polyurethane/modified graphene oxide irradiated by an infrared laser in example 1 of the present invention.
As shown in fig. 7, for the composite materials with three different graphene oxide contents, as the doping concentration thereof is increased, after the infrared laser irradiation is performed for 60s, the temperature of the surface irradiation center is rapidly increased to 83 ℃, 127 ℃ and 149 ℃ respectively. The composite material system realizes excellent photo-thermal conversion capability under the irradiation of infrared laser, and the rapidly raised surface temperature is far higher than the trigger temperature required by the attack stage exchange process of diselenide bonds, thereby having the basis of realizing self-healing capability.
In order to verify the photothermal self-healing characteristics of the composite material, the material which was fractured and subjected to surface laser irradiation was subjected to a tensile test using a mechanical tensile curve, and the results are shown in fig. 8, in which (a), (b), and (c) are infrared thermal imaging diagrams of composite material samples containing 0.7%, 0.9%, and 1.1% modified graphene oxide, respectively.
Fig. 8 is a mechanical tensile curve diagram of the polyurethane/modified graphene oxide sample strip in example 1 of the present invention after irradiation with infrared laser.
As shown in fig. 8, by irradiating the surface of the sample with infrared laser for 60s, the three composite materials can have different degrees of recovery mechanical strength and elongation at break under the condition of complete fracture, and the self-healing rate is significantly improved with the increase of the doping amount of the modified graphene oxide, and the sample containing 1.1% of modified graphene oxide prepared in example 1 reaches the highest self-healing rate of 88.28%, which is consistent with the change rule of the photothermal conversion temperature observed in fig. 7.
By combining the test results, the composite material provided by the invention has good photo-thermal self-healing capability, can realize accurate and efficient self-healing function under the control of infrared laser, and has wide application prospect as a novel functional material.
Effects and effects of the embodiments
According to the composite material with the photo-thermal self-healing function and the preparation method thereof, the hydroxyl-terminated diselenide bond monomer containing the dynamic diselenide bond is synthesized as the chain extender, and then the hydroxyl-terminated diselenide bond monomer is added into a system of diisocyanate solution and dihydric alcohol to obtain a polyurethane system. In the polyurethane system, a hydroxyl-terminated diselenide bond monomer is used as a chain extender to carry out chain extension on polyurethane synthesized by dihydric alcohol and diisocyanate, wherein the dihydric alcohol and the diisocyanate are main bodies of polyurethane chain segments; on the other hand, chemically modifying the graphene oxide prepared by the Hummers method by using diisocyanate, and doping and blending the modified graphene oxide and the prepared polyurethane matrix to obtain the final composite material.
The dynamic diselenide bond has reversibility, and has lower bond energy and more efficient self-healing capacity compared with the common same type of dynamic chemical bonds such as disulfide bond, Diels-Alder bond and the like; the excellent photo-thermal conversion performance of the graphene oxide can endow a matrix with more sensitive photo-thermal response characteristics after doping; meanwhile, the doping blending by the chemical modification method is not simple physical adsorption but stronger chemical bond connection, so that the obtained composite material has good mechanical property and excellent photo-thermal self-healing capability.
The molar ratio of the total amount of the dihydric alcohol to the diisocyanate is 1.0-1.2, and the hydroxyl groups are slightly excessive, so that hydroxyl-terminated polyurethane molecules can be prepared, and a premise is provided for the subsequent reaction with isocyanate groups existing in the modified graphene oxide. The molar ratio of the hydroxyl-terminated diselenide bond monomer to the dihydric alcohol is 0.8-1.0, and an ideal prepolymer molecular weight can be obtained within the ratio range.
The Mn of the dihydric alcohol is one of 2000-4000 dihydroxy terminated Polycaprolactone (PCL), polytetramethylene ether glycol (PTMG) and polypropylene glycol (PPG), and the dihydric alcohol has good flexibility and is beneficial to a self-healing process under a thermal driving condition. The diisocyanate is one of diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI), has moderate reaction activity, and can well react with the terminal hydroxyl of the dihydric alcohol.
The preparation method of the embodiment is economic and convenient, the sources of the used raw materials are wide, the introduction of the diselenide bond can adjust the molecular structure by controlling the feeding proportion of the diselenide bond chain extender monomer and the dihydric alcohol, and further the adjustment of the photothermal sensitivity and the self-healing capacity is realized; the molecular weight of the dihydric alcohol can also be selected according to the requirement of the actual molecular weight of the polyurethane; the selection of the dihydric alcohol and the diisocyanate has diversity, and the mechanical property, hydrophilic property, hydrophobic property and the like of the final product are adjusted; the chemical modification operation of diisocyanate and graphene oxide is convenient, and the content of isocyanic acid radical on the surface of the modified graphene oxide can be adjusted by controlling the feeding amount of the diisocyanate, so that the performance of the composite material is influenced; the polyurethane and the modified graphene oxide are doped and blended conveniently, and the photo-thermal self-healing capacity of the final composite material can be adjusted by controlling the doping proportion. The composite material with the photo-thermal self-healing characteristic can realize remote, accurate and controllable self-healing, which cannot be met by the traditional self-healing material, and has wide prospect for the application in the fields of aerospace, automobile industry and the like.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (8)
1. A preparation method of a composite material with a photo-thermal self-healing function is characterized by comprising the following steps:
step 1, dispersing graphene oxide in a DMF (dimethyl formamide) solution under the atmosphere of inert gas, adding diisocyanate, stirring and reacting at room temperature to obtain a reaction solution, pouring the reaction solution into dichloromethane to obtain a turbid solution, and performing centrifugal separation on the turbid solution to obtain modified graphene oxide;
step 2, adding selenium powder into an aqueous solution of sodium borohydride in an ice bath environment, mixing and stirring, heating to 70-80 ℃, and heating to obtain an aqueous solution of sodium selenide;
step 3, adding the sodium selenide aqueous solution into the 11-bromo-1-undecanol solution under the inert gas atmosphere, heating to 40-60 ℃ for reaction to obtain a light yellow solid, and purifying the light yellow solid to obtain yellow powder, namely a hydroxyl-terminated diselenide bond monomer;
step 4, slowly adding a diisocyanate solution into a dihydric alcohol solution in an inert gas atmosphere, heating and reacting for a period of time, then dropwise adding the hydroxyl-terminated diselenide bond monomer, and continuing to react to obtain a polyurethane product;
and 5, dissolving the modified graphene oxide obtained in the step 1 in a DMF (dimethyl formamide) solution in an inert gas atmosphere, adding the solution into the solution of the polyurethane product, heating and stirring the solution, then carrying out ultrasonic treatment, finally transferring the mixed solution into a mold, and heating the mixed solution to obtain a target product, namely the composite material with the photo-thermal self-healing function.
2. The method for preparing the composite material with photothermal self-healing function according to claim 1, wherein:
wherein the molar ratio of the dihydric alcohol to the diisocyanate is 1.0-1.2,
the molar ratio of the hydroxyl-terminated diselenide bond monomer to the dihydric alcohol is 0.8-1.0.
3. The method for preparing the composite material with photothermal self-healing function according to claim 1, wherein:
the dihydric alcohol is any one of dihydroxy terminated polycaprolactone with Mn of 2000-4000, polytetramethylene ether glycol with Mn of 2000-4000 or polypropylene glycol with Mn of 2000-4000, and the diisocyanate is diphenylmethane diisocyanate or isophorone diisocyanate.
4. The method for preparing the composite material with photothermal self-healing function according to claim 1, wherein:
in the step 1, the mass ratio of the graphene oxide to the diisocyanate is 0.1-0.4.
5. The method for preparing the composite material with photothermal self-healing function according to claim 1, wherein:
in the step 5, the mass of the modified graphene oxide is 0.3-1.5% of the total mass of the diisocyanate, the dihydric alcohol and the hydroxyl-terminated diselenide bond monomer in the step 4.
6. The method for preparing the composite material with photothermal self-healing function according to claim 1, wherein:
wherein, in the step 3, the purification operation of the light yellow solid is as follows: adding dichloromethane in a volume ratio of 4: 1: ethyl acetate is used as eluent, and the yellow powder, namely the hydroxyl-terminated diselenide bond monomer, is obtained by rotary evaporation after purification by a chromatographic column.
7. The method for preparing the composite material with photothermal self-healing function according to claim 1, wherein:
wherein, in the step 4, when the diisocyanate solution is slowly added into the dihydric alcohol solution, dibutyltin dilaurate is added as a catalyst.
8. A composite material with a photothermal self-healing function, which is prepared by the method for preparing a composite material with a photothermal self-healing function according to any one of claims 1 to 7.
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