CN112250878A - Thermally self-repairing recyclable epoxy resin and preparation method thereof - Google Patents
Thermally self-repairing recyclable epoxy resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermally self-repairing recyclable epoxy resin and a preparation method thereof, wherein the thermally self-repairing recyclable epoxy resin is prepared from raw materials including a hexagonal boron nitride-based functional additive, POSS containing furan and linear epoxy oligomer in a mass ratio of 0.5-0.6: 0.1-0.2: 1 through a Diels-Alder reaction. The modified hexagonal boron nitride self-repairing material has low dielectric constant and good thermal conductivity, can meet the requirements of low dielectric constant and high thermal conductivity needed by the field of electronic materials, the low dielectric constant is provided by POSS, the high thermal conductivity is provided by hBN, and the self-repairing and recoverable performance of the epoxy resin is realized by Diels-Alder reverse reaction generated during heating between imide groups contained in the modified hexagonal boron nitride and furan groups in a system.
Description
Technical Field
The invention belongs to the technical field of organic materials, and particularly relates to a thermally self-repairing recyclable epoxy resin and a preparation method thereof.
Background
In the field of electronic and microelectronic materials, in order to accelerate the transmission speed of signals and reduce signal interference and inductive coupling, the development of low dielectric constant materials is urgently needed; in addition, in order to effectively solve the problem of heat generation during the operation of the material, high heat conductivity is also necessary for the material. Polysilsesquioxane (POSS), Si and O elements form a nano-sized cage structure, and the heat resistance is good; the hollow structure can reduce the dielectric constant of the nano composite material due to the introduction of nano-scale air gaps into the polymer matrix; hexagonal boron nitride (hBN) is a material with excellent properties such as high thermal conductivity, high heat resistance, strong lubricity, oxidation resistance, good corrosion resistance and the like, is often used as a functional additive and has wide application in the fields of materials such as heat conduction materials, wear-resistant materials, anticorrosion materials and the like, and in addition, based on the high thermal conductivity, the hBN also plays an important role in the fields of preparing intelligent materials with thermal response, such as thermally self-repairing materials, thermally shape memory materials and the like. Therefore, the combination of POSS and hBN to prepare the material with low dielectric constant and high thermal conductivity has important significance in the fields of electronics and microelectronics. CN 110128821A discloses a bismaleimide-triazine resin with high thermal conductivity and low dielectric constant containing POSS and boron nitride. However, in the system, the used resin is a copolymer of three components, namely cyanate ester resin, bismaleimide and epoxy resin, and the matrix resin does not have the self-repairing performance, the recycling performance and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the thermally self-repairing recyclable epoxy resin.
The invention also aims to provide a preparation method of the thermally self-repairing recyclable epoxy resin.
The technical scheme of the invention is as follows:
a kind of hot self-repairing recoverable epoxy resin, is made by raw materials including hexagonal boron nitride base functional additive (m-hBN-OH), POSS (F-POSS) containing furan and linear epoxy oligomer (FA-DGEBA) with the mass ratio of 0.5-0.6: 0.1-0.2: 1 through Diels-Alder reaction; wherein the content of the first and second substances,
the hexagonal boron nitride-based functional additive is prepared by reacting N- (propyltriethoxysilane) maleimide (Mi-Si) and hydroxylated hexagonal boron nitride (hBN-OH);
the furan-containing POSS is prepared by reacting octaaminophenyl POSS with furfuryl isocyanate;
the linear epoxy oligomer is prepared by reacting Furfuryl Amine (FA) with a diepoxide DGEBA.
In a preferred embodiment of the invention, the mass ratio of the N- (propyltriethoxysilane) maleimide to the hydroxylated hexagonal boron nitride is from 0.5 to 6: 1.
Further preferably, the N- (propyltriethoxysilane) maleimide is prepared from raw materials including 3-aminopropyltriethoxysilane (KH550), maleic anhydride, zinc chloride and hexamethyldisilazane.
Still more preferably, the molar ratio of the 3-aminopropyltriethoxysilane to maleic anhydride is 1: 1.
In a preferred embodiment of the present invention, the molar ratio of the octaaminophenyl POSS to furfuryl isocyanate is from 1: 8.1 to 9.0.
In a preferred embodiment of the invention, the molar ratio of furfuryl amine to diepoxide is 1: 0.5 to 2.
The preparation method of the thermally self-repairing recyclable epoxy resin comprises the following steps:
(1) mixing furfurylamine and a diepoxide DGEBA in DMF, reacting at 110-120 ℃ for 12-24h, stopping the reaction, and removing DMF by rotary evaporation to obtain a linear epoxy oligomer;
(2) mixing 3-aminopropyltriethoxysilane and maleic anhydride, reacting in dichloromethane for 1-2h at room temperature, and performing rotary evaporation to remove dichloromethane after the reaction to obtain an intermediate product; reacting the intermediate product in toluene at 75-85 ℃ for 4-6h in the presence of zinc chloride and hexamethyldisilazane, and filtering and rotary evaporating the obtained reaction product to obtain the N- (propyltriethoxysilane) maleimide;
(3) sintering hexagonal boron nitride in a tubular furnace at 875-910 ℃ for 2.5-3.5h in the presence of water vapor and under the protection of argon, and then performing freeze-drying treatment on the sintered product to obtain hydroxylated hexagonal boron nitride; mixing the N- (propyltriethoxysilane) maleimide prepared in the step (1) and hydroxylated hexagonal boron nitride, reacting for 6-10h in toluene at 90-100 ℃ under the protection of nitrogen, washing and drying the obtained reaction product with ethanol to obtain the hexagonal boron nitride-based functional additive;
(4) dissolving octaaminophenyl POSS in DMF, stirring for 30-40min under the protection of argon, sequentially adding dibutyltin diacetate and furfuryl isocyanate, stirring and mixing uniformly at room temperature, reacting for 2-4H at 50-60 ℃, removing DMF by rotary evaporation after the reaction is finished, dissolving the obtained product in THF, and reacting in excess H for 30-40min2Precipitating and separating for many times in O, and then removing THF in vacuum to obtain the POSS containing furan;
(5) and (2) mixing the linear epoxy oligomer obtained in the step (1), the hexagonal boron nitride-based functional additive obtained in the step (3) and the furan-containing POSS obtained in the step (4) and dissolving in N-methyl-2-pyrrolidone, performing ultrasonic treatment to obtain a mixed solution with the concentration of 30-50 wt%, injecting the mixed solution into a polytetrafluoroethylene mold, curing and reacting for 12-24h at the temperature of 60-80 ℃, and drying the obtained cured product in a vacuum oven to obtain the thermally self-repairing recyclable epoxy resin.
In a preferred embodiment of the present invention, in the step (2), the molar ratio of the intermediate product, zinc chloride and hexamethyldisilazane is from 1: 1 to 2: 1.5.
In a preferred embodiment of the present invention, in the step (3), the ratio of the hydroxylated hexagonal boron nitride to the toluene is 1 g: 30 to 150 mL.
In a preferred embodiment of the present invention, in the step (4), the mass ratio of the octaaminophenyl POSS and the dibutyltin diacetate is 10-20: 1.
The invention has the beneficial effects that:
1. the modified hexagonal boron nitride self-repairing material has low dielectric constant and good thermal conductivity, can meet the requirements of low dielectric constant and high thermal conductivity needed by the field of electronic materials, the low dielectric constant is provided by POSS, the high thermal conductivity is provided by hBN, and the self-repairing and recoverable performance of the epoxy resin is realized by Diels-Alder reverse reaction generated during heating between imide groups contained in the modified hexagonal boron nitride and furan groups in a system.
2. The invention completely carries out crosslinking through Diels-Alder reversible dynamic bonds, so that the thermosetting epoxy resin has good removability, simultaneously solves the problems that the traditional thermosetting epoxy resin cannot be repeatedly processed and is difficult to recover, and is expected to be applied in the field of self-repairing, removable and recyclable materials.
Drawings
FIG. 1 is a diagram showing the synthesis reaction of FA-DGEBA in the example of the present invention.
FIG. 2 is a reaction diagram of Mi-Si synthesis in an example of the present invention.
FIG. 3 is a diagram showing the reaction for synthesizing m-hBN-OH in the example of the present invention.
FIG. 4 is a diagram of the synthesis of F-POSS in an example of the present invention.
FIG. 5 is a reaction diagram illustrating the synthesis of the thermally self-healing recyclable epoxy resin according to an embodiment of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, the self-repairing performance and the recycling performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 1.
TABLE 1
Example 2:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 27.36g (0.08mol) of DGEBA and 35mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2Precipitating in O, separating, and weighingAnd repeating the steps for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-2 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recoverable epoxy resin prepared by the embodiment are shown in table 2.
TABLE 2
Example 3:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.1g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1 hour, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 1.6gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 90 ℃ under the protection of nitrogen and reacted for 10 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-3 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recoverable epoxy resin prepared by the embodiment are shown in table 3.
TABLE 3
Example 4:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 40mL dmdf is added, stirring is carried out for 40min under the protection of argon, 0.06g of dibutyltin diacetate and 1.11g (9.0mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 60 ℃, the reaction is carried out for 3h, and the reaction is stopped after cooling; the solvent was removed by rotary evaporation and the product was dissolved in 5mL of HF at 50mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-4 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 4.
TABLE 4
Example 5:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in FIG. 4, 1.16g (1mmol) of octaaminophenyl POSS was weighed into a 100mL two-necked flask, 30mL of DMF was added, stirring was carried out under argon atmosphere for 30min, and 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of iso-butyl alcohol were added in that orderUniformly stirring and mixing the furfuryl cyanate at room temperature, heating to 55 ℃, reacting for 2 hours, and cooling to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.6gm-hBN-OH and 0.4g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 20 hours at 80 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-5 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 5.
TABLE 5
Example 6:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.4gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 6.
TABLE 6
Example 7:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 4.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL of HF at 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 7.
TABLE 7
Example 8:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.32gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in FIG. 4, 1.16g (1mmol) of octaaminophenyl POSS was weighed into a 100mL two-necked flask, 30mL of DMF was added, stirring was carried out under argon atmosphere for 30min, and 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of iso-butyl alcohol were added in that orderUniformly stirring and mixing the furfuryl cyanate at room temperature, heating to 55 ℃, reacting for 2 hours, and cooling to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recoverable epoxy resin prepared by the embodiment are shown in table 8.
TABLE 8
Example 9:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 5.6gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 9.
TABLE 9
Example 10:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 8.55g (0.025mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 10.
Watch 10
Example 11:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 34.20g (0.1mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in FIG. 4, 1.16g (1mmol) of octaaminophenyl POSS was weighed into a 100mL two-necked flask, 30mL of DMF was added, stirring was carried out under argon atmosphere for 30min, and 0.1g of dibutyltin diacetate and 1.0g (8.1 mm) of dibutyltin diacetate were added in that orderol) furfuryl isocyanate, stirring and mixing uniformly at room temperature, heating to 55 ℃, reacting for 2 hours, and cooling to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 11.
TABLE 11
Example 12:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 6.84g (0.02mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 12.
TABLE 12
Example 13:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 42.78g (0.13mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.0g (8.1mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 13.
Watch 13
Example 14:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in FIG. 4, 1.16g (1mmol) of octaaminophenyl POSS was weighed into a 100mL two-necked flask, 30mL of DMF was added, stirred under argon for 30min, and then 0.1g of dibutyltin diacetate, 1, was added.05g (8.5mmol) of furfuryl isocyanate, stirring and mixing uniformly at room temperature, heating to 55 ℃, reacting for 2 hours, and cooling to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 14.
TABLE 14
Example 15:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 0.86g (7.0mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 15.
Watch 15
Example 16:
(1) as shown in FIG. 1, 4.85mL (0.05mol) of FA, 17.10g (0.05mol) of DGEBA and 50mL of DMF were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;
(2) as shown in FIG. 2, 1.9mL (8.14mmol) of KH550, 0.8g (8.14mmol) of maleic anhydride, and 100mL of dichloromethane were added to a 250mL single-neck flask and reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain an intermediate product; adding the obtained intermediate product and 80mL of toluene into a 250mL three-necked bottle, uniformly mixing under the nitrogen atmosphere, weighing 1.2g of zinc chloride, adding the zinc chloride into the three-necked bottle, heating to 80 ℃, weighing 1.97g of hexamethyldisilazane (12.21mmol) to be dissolved in 20mL of toluene, adding the hexamethyldisilazane into a constant-pressure dropping funnel, dropwise adding, adjusting the dropping speed, completing the dropwise adding within half an hour, reacting for 4 hours, stopping the reaction, and performing suction filtration and rotary evaporation on the product to obtain Mi-Si.
(3) As shown in fig. 3, the hBN is fired in a tube furnace under the protection of argon gas in the presence of water vapor at 900 ℃ for 3h, and then is subjected to freeze-drying treatment for 24h to obtain hydroxylated hBN, namely hBN-OH; 0.8g of hBN-OH and 0.8gMi-Si are added into a 250mL three-necked bottle, 100mL of toluene is added, and the mixture is condensed and refluxed at 100 ℃ under the protection of nitrogen and reacts for 8 hours. Washing and drying the product by ethanol to obtain m-hBN-OH.
(4) As shown in fig. 4, 1.16g (1mmol) of octaaminophenyl POSS is weighed and added into a 100mL double-neck flask, 30mL of dmf is added, stirring is carried out for 30min under the protection of argon, 0.1g of dibutyltin diacetate and 1.23g (10mmol) of furfuryl isocyanate are sequentially added, stirring and mixing are carried out at room temperature, the temperature is raised to 55 ℃, reaction is carried out for 2h, and cooling is carried out to stop the reaction; the solvent was removed by rotary evaporation and the product was dissolved in 5mL THF in 25mL H2And precipitating in O, separating, repeating for three times, and removing the solvent in vacuum to obtain the F-POSS.
(5) As shown in FIG. 5, 3g of FA-DGEBA, 1.5gm-hBN-OH and 0.5g of F-POSS are dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with the concentration of 30 wt%, after ultrasonic treatment for a period of time, the mixture is injected into a polytetrafluoroethylene mold, curing reaction is carried out for 12 hours at the temperature of 60 ℃, and after a cured product is dried in a vacuum oven, the self-repairing thermal recoverable epoxy resin EP-1 is prepared.
Cutting a notch with the height of 70% of the sample strip, heating at 140 ℃ for 4h, testing the mechanical property of the repaired sample strip, and defining the ratio of the tensile strength of the repaired sample strip to the initial tensile strength as repair efficiency; and shearing the cured resin sample strips, heating at 140 ℃ for 4h, and recycling the molded sample strips for related performance tests. The testing performance, self-repairing performance and recovery performance of the thermally self-repairing recyclable epoxy resin prepared by the embodiment are shown in table 16.
TABLE 16
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A thermally self-repairing recyclable epoxy resin is characterized in that: is prepared by the raw materials including hexagonal boron nitride-based functional additive, POSS containing furan and linear epoxy oligomer with the mass ratio of 0.5-0.6: 0.1-0.2: 1 through Diels-Alder reaction; wherein the content of the first and second substances,
the hexagonal boron nitride-based functional additive is prepared by reacting N- (propyltriethoxysilane) maleimide with hydroxylated hexagonal boron nitride;
the furan-containing POSS is prepared by reacting octaaminophenyl POSS with furfuryl isocyanate;
the linear epoxy oligomer is prepared by reacting furfuryl amine with a diepoxide DGEBA.
2. The thermally self-healing recyclable epoxy resin of claim 1, wherein: the mass ratio of the N- (propyltriethoxysilane) maleimide to the hydroxylated hexagonal boron nitride is 0.5-6: 1.
3. The thermally self-healing recyclable epoxy resin of claim 2, wherein: the N- (propyltriethoxysilane) maleimide is prepared from raw materials including 3-aminopropyltriethoxysilane, maleic anhydride, zinc chloride and hexamethyldisilazane.
4. The thermally self-healing recyclable epoxy resin of claim 3, wherein: the molar ratio of the 3-aminopropyltriethoxysilane to the maleic anhydride is 1: 1.
5. The thermally self-healing recyclable epoxy resin of claim 1, wherein: the mol ratio of the octaaminophenyl POSS to the furfuryl isocyanate is 1: 8.1-9.0.
6. The thermally self-healing recyclable epoxy resin of claim 1, wherein: the molar ratio of the furfuryl amine to the diepoxide is 1: 0.5-2.
7. The preparation method of the thermally self-repairing recyclable epoxy resin as claimed in any one of claims 1 to 6, wherein the preparation method comprises the following steps: the method comprises the following steps:
(1) mixing furfurylamine and a diepoxide DGEBA in DMF, reacting at 110-120 ℃ for 12-24h, stopping the reaction, and removing DMF by rotary evaporation to obtain a linear epoxy oligomer;
(2) mixing 3-aminopropyltriethoxysilane and maleic anhydride, reacting in dichloromethane for 1-2h at room temperature, and performing rotary evaporation to remove dichloromethane after the reaction to obtain an intermediate product; reacting the intermediate product in toluene at 75-85 ℃ for 4-6h in the presence of zinc chloride and hexamethyldisilazane, and filtering and rotary evaporating the obtained reaction product to obtain the N- (propyltriethoxysilane) maleimide;
(3) sintering hexagonal boron nitride in a tubular furnace at 875-910 ℃ for 2.5-3.5h in the presence of water vapor and under the protection of argon, and then performing freeze-drying treatment on the sintered product to obtain hydroxylated hexagonal boron nitride; mixing the N- (propyltriethoxysilane) maleimide prepared in the step (1) and hydroxylated hexagonal boron nitride, reacting for 6-10h in toluene at 90-100 ℃ under the protection of nitrogen, washing and drying the obtained reaction product with ethanol to obtain the hexagonal boron nitride-based functional additive;
(4) dissolving octaaminophenyl POSS in DMF, stirring for 30-40min under the protection of argon, sequentially adding dibutyltin diacetate and furfuryl isocyanate, stirring and mixing uniformly at room temperature, reacting for 2-4H at 50-60 ℃, removing DMF by rotary evaporation after the reaction is finished, dissolving the obtained product in THF, and reacting in excess H for 30-40min2Precipitating and separating for many times in O, and then removing THF in vacuum to obtain the POSS containing furan;
(5) and (2) mixing the linear epoxy oligomer obtained in the step (1), the hexagonal boron nitride-based functional additive obtained in the step (3) and the furan-containing POSs obtained in the step (4), dissolving in N-methyl-2-pyrrolidone, performing ultrasonic treatment to obtain a mixed solution with the concentration of 30-50 wt%, injecting the mixed solution into a polytetrafluoroethylene mold, curing and reacting for 12-24h at the temperature of 60-80 ℃, and drying the obtained cured product in a vacuum oven to obtain the thermally self-repairing recyclable epoxy resin.
8. The method of claim 7, wherein: in the step (2), the molar ratio of the intermediate product, the zinc chloride and the hexamethyldisilazane is 1: 1-2: 1.5.
9. The method of claim 7, wherein: in the step (3), the ratio of the hydroxylated hexagonal boron nitride to the toluene is 1 g: 30-150 mL.
10. The method of claim 7, wherein: in the step (4), the mass ratio of the octaaminophenyl POSS to the dibutyltin diacetate is 10-20: 1.
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