CN112250878B - A kind of thermally induced self-healing recyclable epoxy resin and preparation method thereof - Google Patents

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

A kind of thermally induced self-healing recyclable epoxy resin and preparation method thereof

technical field

The invention belongs to the technical field of organic materials, and in particular relates to a thermally induced self-healing recyclable epoxy resin and a preparation method thereof.

Background technique

In the field of electronic and microelectronic materials, in order to speed up signal transmission, reduce signal interference and inductive coupling, it is urgent to develop materials with low dielectric constant; in addition, in order to effectively solve the problem of heat generation when materials work, high thermal conductivity is also such material required. Polysilsesquioxane (POSS), Si and O elements form a nano-sized cage structure with good heat resistance; its hollow structure, due to the ability to introduce nano-scale air gaps into the polymer matrix, can reduce nano Dielectric constant of composite materials; hexagonal boron nitride (hBN) is a kind of material with excellent properties such as high thermal conductivity, high heat resistance, strong lubricity, oxidation resistance, good corrosion resistance, etc. It is used as a functional additive and has a wide range of applications in thermal conductive materials, wear-resistant materials, anti-corrosion materials and other materials. In addition, based on its high thermal conductivity, hBN is used in the preparation of thermally responsive smart materials, such as thermally induced self-healing materials. , thermal shape memory materials and other fields also play an important role. Therefore, the preparation of materials with low dielectric constant and high thermal conductivity by combining POSS and hBN is of great significance in the fields of electronics and microelectronics. CN 110128821 A discloses a bismaleimide-triazine resin containing POSS and boron nitride with high thermal conductivity and low dielectric constant. However, in this system, the resin used is a three-component copolymer of cyanate ester resin, bismaleimide and epoxy resin, and the matrix resin does not have the properties of self-healing and recyclability.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the defects of the prior art and provide a thermally induced self-healing recyclable epoxy resin.

Another object of the present invention is to provide a method for preparing the above thermally induced self-healing recyclable epoxy resin.

The technical scheme of the present invention is as follows:

A thermally induced self-healing recyclable epoxy resin, comprising a hexagonal boron nitride-based functional additive (m-hBN-OH), a furan-containing POSS (F- POSS) and linear epoxy oligomers (FA-DGEBA) are prepared by Diels-Alder reaction; wherein,

The above-mentioned hexagonal boron nitride-based functional additive is prepared by the reaction of N-(propyltriethoxysilane) maleimide (Mi-Si) and hydroxylated hexagonal boron nitride (hBN-OH);

The above-mentioned furan-containing POSS is obtained by the reaction of octaaminophenyl POSS and furfuryl isocyanate;

The above-mentioned linear epoxy oligomers are prepared by reacting furfurylamine (FA) and diepoxy compound DGEBA.

In a preferred embodiment of the present invention, the mass ratio of the N-(propyltriethoxysilane)maleimide to the hydroxylated hexagonal boron nitride is 0.5-6:1.

Further preferably, the N-(propyl triethoxy silane) maleimide is composed of 3-aminopropyl triethoxy silane (KH550), maleic anhydride, zinc chloride and hexamethyl dimethide Made from raw materials including silazane.

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 octaaminophenyl POSS to furfuryl isocyanate is 1:8.1-9.0.

In a preferred embodiment of the present invention, the molar ratio of the furfurylamine and the diepoxy compound is 1:0.5-2.

The preparation method of the above-mentioned thermally induced self-healing recyclable epoxy resin comprises the following steps:

(1) mixing furfurylamine and diepoxy compound DGEBA in DMF, reacting at 110-120° C. for 12-24 hours, then stopping the reaction, and removing DMF by rotary evaporation to obtain a linear epoxy oligomer;

(2) Mix 3-aminopropyltriethoxysilane and maleic anhydride, react in dichloromethane for 1-2h at room temperature, and then rotate to remove the dichloromethane after the reaction to obtain an intermediate product; the intermediate product is in In the presence of zinc chloride and hexamethyldisilazane, the reaction is carried out in toluene at 75-85 ° C for 4-6 h, and the obtained reaction product is filtered and rotary evaporated to obtain the N-(propyltriethoxy silane) maleimide;

(3) The hexagonal boron nitride is fired for 2.5-3.5 h in a tube furnace at 875-910 ° C in the presence of water vapor and under the protection of argon, and then the fired product is subjected to freeze-drying treatment to obtain Hydroxylated hexagonal boron nitride; mix the N-(propyltriethoxysilane) maleimide obtained in step (1) and the hydroxylated hexagonal boron nitride, and heat in toluene at 90-100° C. The reaction is carried out under nitrogen protection for 6-10 hours, and the obtained reaction product is washed with ethanol and dried to obtain the hexagonal boron nitride-based functional additive;

(4) Dissolve octaaminophenyl POSS in DMF, stir under the protection of argon for 30-40min, then add dibutyltin diacetate and furfuryl isocyanate in turn, stir and mix at room temperature, and stir at room temperature for 50-60 min. The reaction is carried out at ℃ for 2-4 h. After the reaction is completed, the DMF is removed by rotary evaporation. The obtained product is dissolved in THF, precipitated and separated in excess H ₂ O for several times, and then the THF is removed in vacuo to obtain the furan-containing POSS;

(5) The linear epoxy oligomer obtained in step (1), the hexagonal boron nitride-based functional additive obtained in step (3) and the furan-containing POSS obtained in step (4) are mixed and dissolved in N-methyl- 2-pyrrolidone, after ultrasonic treatment, a mixed solution with a concentration of 30-50 wt% is obtained, the mixed solution is injected into a polytetrafluoroethylene mold, and cured at 60-80 ° C for 12-24 hours, and the obtained cured product is dried in a vacuum oven. , that is, the thermally induced self-healing recyclable epoxy resin is obtained.

In a preferred embodiment of the present invention, in the step (2), the molar ratio of the intermediate product, zinc chloride and hexamethyldisilazane is 1:1-2:1.5.

In a preferred embodiment of the present invention, in the step (3), the ratio of the hydroxylated hexagonal boron nitride to toluene is 1 g:30-150 mL.

In a preferred embodiment of the present invention, in the step (4), the mass ratio of the octaaminophenyl POSS and dibutyltin diacetate is 10-20:1.

The beneficial effects of the present invention are:

1. The present invention has low dielectric constant and good thermal conductivity and can meet the requirements of low dielectric constant and high thermal conductivity required in the field of electronic materials. The low dielectric constant is provided by POSS, the high thermal conductivity is provided by hBN, and epoxy resin is provided. The self-healing and recyclable properties of the modified hexagonal boron nitride are realized by the Diels-Alder reverse reaction between the imide group contained in the modified hexagonal boron nitride and the furan group in the system during heating.

2. The present invention is completely cross-linked through Diels-Alder reversible dynamic bonds, so that it has good removability, and at the same time solves the problems that traditional thermosetting epoxy resins cannot be processed repeatedly and are difficult to recycle. The field of removable, recyclable materials is applied.

Description of drawings

Fig. 1 is the synthesis reaction diagram of FA-DGEBA in the embodiment of the present invention.

Fig. 2 is the synthesis reaction diagram of Mi-Si in the embodiment of the present invention.

Fig. 3 is the synthesis reaction diagram of m-hBN-OH in the embodiment of the present invention.

Fig. 4 is the synthesis reaction diagram of F-POSS in the embodiment of the present invention.

FIG. 5 is a synthesis reaction diagram of the thermally induced self-healing recyclable epoxy resin in the embodiment of the present invention.

Detailed ways

The technical solutions of the present invention will be further illustrated and described below through specific embodiments in conjunction with the accompanying drawings.

Example 1:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 1.

Table 1

Example 2:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 27.36g (0.08mol) DGEBA, 35mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-2 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 2.

Table 2

Example 3:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.1g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) as shown in Figure 2, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane in a 250mL single-necked flask and react at room temperature for 1h, remove the solvent by rotary evaporation to obtain an intermediate product ; Add the obtained intermediate product and 80 mL of toluene in a 250mL there-necked flask, mix well under a nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 1.6g Mi-Si into a 250mL three-neck flask, add 100mL toluene, condense and reflux at 90°C under nitrogen protection, and react for 10h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-3 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 3.

table 3

Example 4:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 40mL DMF, stir under argon protection for 40min, add 0.06g dibutyltin diacetate successively, 1.11g (9.0 mmol) furfuryl isocyanate, stirred and mixed evenly at room temperature, heated to 60 °C, reacted for 3 h, cooled to stop the reaction; rotary evaporated to remove the solvent, then the product was dissolved in 5 mL of THF, precipitated in 50 mL of H ₂ O, and separated. , repeated three times, and the solvent was removed in vacuo to obtain F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-4 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 4.

Table 4

Example 5:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3 g of FA-DGEBA, 1.6 gm-hBN-OH and 0.4 g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30 wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold, and cured at 80° C. for 20 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-5 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 5.

table 5

Example 6:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.4g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 6.

Table 6

Example 7:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 4.8g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF, precipitated in 25 mL of H ₂ O, and separated. , repeated three times, and the solvent was removed in vacuo to obtain F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 7.

Table 7

Example 8:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.32g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 8.

Table 8

Example 9:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 5.6g Mi-Si to a 250mL three-neck flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 9.

Table 9

Example 10:

(1) as shown in Figure 1, add 4.85mL (0.05mol) FA, 8.55g (0.025mol) DGEBA, 50mL DMF in a 250mL single-necked flask at room temperature for 1h, and remove the solvent by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 10.

Table 10

Example 11:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 34.20g (0.1mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 11.

Table 11

Example 12:

(1) as shown in Figure 1, add 4.85mL (0.05mol) FA, 6.84g (0.02mol) DGEBA, 50mL DMF at room temperature in 250mL single-neck flask, react 1h at room temperature, remove the solvent by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; Add the obtained intermediate product and 80 mL of toluene in a 250mL there-necked flask, mix well under a nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-neck flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 12.

Table 12

Example 13:

(1) as shown in Figure 1, add 4.85mL (0.05mol) FA, 42.78g (0.13mol) DGEBA, 50mL DMF in a 250mL single-necked flask at room temperature for 1h, remove the solvent by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-neck flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.0g (8.1 mmol) of furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the formed strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 13.

Table 13

Example 14:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) octaaminophenyl POSS and add it to a 100mL double-necked flask, add 30mL DMF, stir under argon protection for 30min, add 0.1g dibutyltin diacetate successively, 1.05g (8.5 mmol) furfuryl isocyanate, stirred and mixed at room temperature, heated to 55°C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 14.

Table 14

Example 15:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant-pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-neck flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) of octaaminophenyl POSS into a 100mL double-necked flask, add 30mL DMF, stir under argon protection for 30min, add 0.1g dibutyltin diacetate successively, 0.86g (7.0 mmol) furfuryl isocyanate, stirred and mixed evenly at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; evaporated to remove the solvent, then the product was dissolved in 5 mL of THF, and precipitated in 25 mL of H ₂ O, The separation was repeated three times and the solvent was removed in vacuo to give F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 15.

Table 15

Example 16:

(1) As shown in Figure 1, 4.85mL (0.05mol) FA was added in a 250mL single-neck flask, 17.10g (0.05mol) DGEBA, 50mL DMF were reacted at room temperature for 1h, and the solvent was removed by rotary evaporation to obtain FA-DGEBA;

(2) As shown in Figure 2, in a 250mL single-necked flask, add 1.9mL (8.14mmol) KH550, 0.8g (8.14mmol) maleic anhydride, 100mL dichloromethane react at room temperature for 1h, and remove the solvent by rotary evaporation to obtain an intermediate product ; In a 250mL there-necked flask, add the obtained intermediate product and 80mL of toluene, mix homogeneously under nitrogen atmosphere, weigh 1.2g of zinc chloride and add it to the there-necked flask, raise the temperature to 80°C, weigh 1.97g of hexamethyldisilazane (12.21 mmol) was dissolved in 20 mL of toluene, added to a constant pressure dropping funnel, added dropwise, and the dripping rate was adjusted, and the addition was completed within half an hour, and the reaction was stopped for 4 h. Get Mi-Si.

(3) As shown in Figure 3, hBN was fired in a tube furnace in the presence of water vapor, under the protection of argon, at 900 °C for 3 h, and lyophilized for 24 h to obtain hydroxylated hBN, that is, hBN-OH; add 0.8ghBN-OH and 0.8g Mi-Si into a 250mL three-necked flask, add 100mL toluene, condense and reflux at 100°C under nitrogen protection, and react for 8h. The product was washed with ethanol and dried to give m-hBN-OH.

(4) As shown in Figure 4, weigh 1.16g (1mmol) of octaaminophenyl POSS into a 100mL double-necked flask, add 30mL DMF, stir for 30min under argon protection, add 0.1g dibutyltin diacetate successively, 1.23g (10 mmol) furfuryl isocyanate, stirred and mixed at room temperature, heated to 55 °C, reacted for 2 h, cooled to stop the reaction; the solvent was removed by rotary evaporation, and the product was dissolved in 5 mL of THF, precipitated in 25 mL of H ₂ O, and separated. , repeated three times, and the solvent was removed in vacuo to obtain F-POSS.

(5) As shown in Figure 5, 3g FA-DGEBA, 1.5gm-hBN-OH and 0.5g F-POSS were dissolved in N-methyl-2-pyrrolidone to obtain a reactant solution with a concentration of 30wt%, and ultrasonically treated After a period of time, the mixture was injected into a polytetrafluoroethylene mold and cured at 60° C. for 12 hours. After the cured product was dried in a vacuum oven, the thermally induced self-healing recyclable epoxy resin EP-1 was prepared.

The spline was cut with a notch of 70% of the height, heated at 140 °C for 4 hours, and the mechanical properties of the repaired spline were tested again, and the ratio of the repaired spline tensile strength to the initial tensile strength was defined as the repair efficiency; The cured resin strips were cut into pieces, heated at 140 °C for 4 h, and the shaped strips were recovered and used for relevant performance tests. The test performance, self-healing and recycling performance of the thermally induced self-healing recyclable epoxy resin prepared in this example are shown in Table 16.

Table 16

The above descriptions are only preferred embodiments of the present invention, so the scope of implementation of the present invention cannot be limited accordingly. That is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the description should still be covered by the present invention. In the range.

Claims (1)

1. a preparation method of thermally induced self-repairing recyclable epoxy resin, is characterized in that: comprise the steps: (1) Mix furfuryl amine and diepoxy compound DGEBA in DMF at a molar ratio of 1:0.5-2, react at 110-120 °C for 12-24 hours, stop the reaction, and remove DMF by rotary evaporation to obtain a linear epoxy oligomer thing; (2) Mix 3-aminopropyltriethoxysilane and maleic anhydride in a molar ratio of 1:1, react in dichloromethane for 1-2 hours at room temperature, and then remove the dichloromethane by rotary evaporation to obtain an intermediate product; the intermediate product was reacted in toluene at 75-85 °C for 4-6 h in the presence of zinc chloride and hexamethyldisilazane, and the obtained reaction product was filtered and rotary evaporated to obtain N-( propyltriethoxysilane) maleimide; the molar ratio of the intermediate product, zinc chloride and hexamethyldisilazane is 1:1-2:1.5; (3) Hexagonal boron nitride is fired in a tube furnace at 875-910°C for 2.5-3.5 hours in the presence of water vapor and under the protection of argon, and then the fired product is subjected to freeze-drying treatment to obtain Hydroxylated hexagonal boron nitride; mix the N-(propyltriethoxysilane) maleimide obtained in step (1) and the hydroxylated hexagonal boron nitride, in toluene at 90-100 ℃ and The reaction is carried out for 6-10h under nitrogen protection, and the obtained reaction product is washed with ethanol and dried to obtain a hexagonal boron nitride-based functional additive; the ratio of the hydroxylated hexagonal boron nitride to toluene is 1g: 30-150mL; (4) Dissolve octaaminophenyl POSS in DMF, stir for 30-40min under argon protection, then add dibutyltin diacetate and furfuryl isocyanate in turn, stir and mix at room temperature, and place at 50-60 The reaction was carried out at ℃ for 2-4 h. After the reaction was completed, DMF was removed by rotary evaporation. The obtained product was dissolved in THF, precipitated and separated in excess H ₂ O for several times, and then THF was removed in vacuo to obtain furan-containing POSS; octaaminophenyl The mol ratio of POSS and furfuryl isocyanate is 1: 8.1-9.0; the mass ratio of octaaminophenyl POSS and dibutyltin diacetate is 10-20: 1; (5) The linear epoxy oligomer obtained in step (1), the hexagonal boron nitride-based functional additive obtained in step (3) and the furan-containing POSS obtained in step (4) are mixed and dissolved in N-methyl- 2-pyrrolidone, after ultrasonic treatment, a mixed solution with a concentration of 30-50wt% is obtained, the mixed solution is injected into a polytetrafluoroethylene mold, and cured at 60-80 ° C for 12-24 hours, and the obtained cured product is dried in a vacuum oven. , that is, the thermally induced self-healing recyclable epoxy resin is obtained.

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