Flexible high polymer material with self-repairing performance and preparation method thereof

Abstract

The application discloses a flexible high polymer material with self-repairing performance and a preparation method thereof. The preparation method of the flexible high polymer material with self-repairing performance comprises the following steps: (1) taking caprolactone and 1,4,8-trioxaspiro-[4,6]-9-undecanone as raw materials, and reacting under the action of a catalyst to obtain a prepolymer; (2) taking the prepolymer and a polyhydric alcohol to react, and after the reaction is completed, pouring the reaction product into a mold, and obtaining the flexible high polymer material with self-repairing performance after solidification. The flexible high polymer material with self-repairing performance has good tensile stress, high tensile strength and small contact angle, so that the service life of the material can be greatly prolonged and chemical pollution can be reduced. In addition, the flexible high polymer material with self-repairing performance has a hydrophilic surface, and can be used as a good base material to develop wearable electronic skin with excellent mechanical properties and self-repairing performance.

Description

Technical Field

[0001] This invention relates to the field of polymer material preparation technology, specifically to a flexible polymer material with self-healing properties and its preparation method. Background Technology

[0002] Self-healing polymers have the ability to repair damage on their own, which not only extends their service life and improves safety, but also reduces material consumption and maintenance costs, making them a material with excellent application potential in wearable and implantable electronics, smart coatings and durable sensors.

[0003] Currently, in order to explore self-healing polymer materials closely related to practical needs, the development trend of the entire self-healing system is gradually shifting from extrinsic self-healing polymers to intrinsic self-healing polymers, from weak gels to tough elastomers with strong mechanical properties, and from harmful solvent dispersions to environmentally friendly aqueous dispersion systems. However, despite the great progress made in this emerging field, preparing self-healing polymers with sufficient mechanical properties remains challenging.

[0004] Therefore, developing a flexible polymer material with good mechanical properties and self-healing capabilities has important application prospects. Summary of the Invention

[0005] In order to overcome at least one of the technical problems existing in the prior art, the present invention first provides a flexible polymer material with self-healing properties.

[0006] The technical solution described in this invention is as follows:

[0007] This invention first provides a method for preparing a flexible polymer material with self-healing properties, characterized by comprising the following steps:

[0008] (1) Using caprolactone and 1,4,8-trioxerospiro-[4,6]-9-undecaneone as raw materials, a prepolymer was obtained by reaction under the action of a catalyst;

[0009] (2) Take the prepolymer and react it with the polyol. After the reaction is completed, pour the reaction product into the mold and solidify it to obtain the flexible polymer material with self-healing properties.

[0010] The inventors made a surprising discovery during their research: the prepolymer prepared from caprolactone and 1,4,8-trioxero-[4,6]-9-undecaneone, and then further reacted with polyols to prepare a flexible polymer material with self-healing properties, can significantly increase the tensile stress of the flexible polymer material with self-healing properties compared to the flexible polymer material with self-healing properties prepared without the addition of polyols. At the same time, it can also reduce the contact angle of the flexible polymer material with self-healing properties, which is beneficial to improving its biocompatibility.

[0011] Preferably, in step (1), the mass ratio of caprolactone to 1,4,8-trioxspiro-[4,6]-9-undecaneone is 3 to 5:1.

[0012] Most preferably, in step (1), the mass ratio of caprolactone to 1,4,8-trioxero-[4,6]-9-undecaneone is 4:1.

[0013] Preferably, the catalyst in step (1) is Sn(Oct)2.

[0014] Preferably, the mass amount of catalyst used in step (1) is 1 to 5% of the total mass of the raw materials caprolactone and 1,4,8-trioxero-[4,6]-9-undecane.

[0015] Most preferably, the mass of the catalyst used in step (1) is 3% of the total mass of the raw materials caprolactone and 1,4,8-trioxero-[4,6]-9-undecane.

[0016] Preferably, the reaction in step (1) refers to reacting at 55-65°C for 1-3 hours, and then heating to 100-120°C under a vacuum of 0.001Pa to continue the reaction for 16-30 hours.

[0017] Most preferably, the reaction in step (1) refers to reacting at 60°C for 2 hours, and then heating to 115°C under a vacuum of 0.001Pa to continue the reaction for 24 hours.

[0018] Preferably, in step (2), the mass ratio of the prepolymer to the polyol is 75-95:25-5.

[0019] Preferably, the reaction described in step (2) refers to a reaction at 65-75°C for 1-3 hours.

[0020] Most preferably, the reaction described in step (2) refers to a reaction at 70°C for 2 hours.

[0021] Preferably, the polyol in step (2) is prepared by the following method:

[0022] Take epoxidized vegetable oil and (3-aminophenyl)boronic acid, and then heat them to react; after the reaction is complete, take the product to obtain the polyol.

[0023] The inventors would like to emphasize that the selection of polyols is crucial in the preparation of self-healing flexible polymer materials. Studies have shown that the polyols prepared from epoxidized vegetable oils and (3-aminophenyl)boronic acid in this invention can significantly increase the tensile stress of the prepared self-healing flexible polymer materials. At the same time, it can also reduce the contact angle of the prepared self-healing flexible polymer materials, which is beneficial to improving their biocompatibility.

[0024] Preferably, the molar ratio of epoxidized vegetable oil to (3-aminophenyl)boronic acid is 1:1 to 1.5.

[0025] Most preferably, the molar ratio of epoxidized vegetable oil to (3-aminophenyl)boronic acid is 1:1.2.

[0026] Preferably, the reaction refers to stirring at 90–110°C for 40–80 minutes;

[0027] Most preferably, the reaction refers to stirring at 100°C for 60 minutes.

[0028] Preferably, the epoxidized vegetable oil is selected from one or more of epoxidized soybean oil, epoxidized corn oil, epoxidized rapeseed oil, epoxidized olive oil, and epoxidized flaxseed oil.

[0029] The present invention also provides a flexible polymer material with self-healing properties prepared by the above preparation method.

[0030] Beneficial Effects: This invention provides a novel method for preparing a flexible polymer material with self-healing properties. The flexible polymer material with self-healing properties described in this invention exhibits good tensile stress, high tensile strength, and a small contact angle; therefore, it can significantly extend the material's service life and reduce chemical pollution. Furthermore, the flexible polymer material with self-healing properties of this invention has a hydrophilic surface and can also serve as a good substrate for developing wearable electronic skin with excellent mechanical properties and self-healing capabilities. Attached Figure Description

[0031] Figure 1 The mechanical properties of the self-healing flexible polymer material of this invention are characterized.

[0032] Figure 2 The self-healing properties of the flexible polymer material with self-healing properties are described in this invention.

[0033] Figure 3This refers to the water contact angle of the flexible polymer material with self-healing properties according to the present invention. Detailed Implementation

[0034] The present invention will be further explained below with reference to specific embodiments, but the embodiments do not limit the present invention in any way.

[0035] Example 1: Preparation of flexible polymer materials with self-healing properties

[0036] (1) Caprolactone and 1,4,8-trioxero-[4,6]-9-undecaneone were mixed in a round-bottom flask at a mass ratio of 4:1 under N2 atmosphere to obtain a mixture. Sn(Oct)2 dissolved in anhydrous toluene was then added to the mixture. The reaction was first carried out at 60°C for 2 hours, and then heated to 115°C under 0.001 Pa vacuum and continued for 24 hours. The reaction mixture was cooled to room temperature and extracted with dichloromethane (DCM). The residue was then removed by centrifugation to obtain the prepolymer.

[0037] (2) Dissolve the prepolymer and polyol in tetrahydrofuran at a mass ratio of 95:5 and react at 70°C for 2 hours. Finally, pour the reaction mixture into a polytetrafluoroethylene mold and remove the solvent at 75°C to cure, thereby obtaining a flexible polymer material with self-healing properties.

[0038] The polyol was prepared by the following method: epoxidized soybean oil and (3-aminophenyl)boronic acid (ABa) were added to a round-bottom flask in a molar ratio of 1:1.2 and stirred at 100°C for 60 minutes; the reactants were cooled to room temperature, extracted with ethyl acetate and washed with saturated NaCl solution; finally, ethyl acetate was removed by rotary evaporation to obtain the polyol.

[0039] Example 2: Only the mass fractions of prepolymer and polyol in step (2) of Example 1 were changed (90:10), and the other parameters and steps were the same as in Example 1.

[0040] Example 3: Only the mass fractions of prepolymer and polyol in step (2) of Example 1 were changed (85:15), and the other parameters and steps were the same as in Example 1.

[0041] Example 4: Only the mass fractions of prepolymer and polyol in step (2) of Example 1 were changed (80:20), and the other parameters and steps were the same as in Example 1.

[0042] Example 5: Only the mass fractions of prepolymer and polyol in step (2) of Example 1 were changed (75:25), and the other parameters and steps were the same as in Example 1.

[0043] Comparative Example 1: Preparation of Flexible Polymer Materials

[0044] Caprolactone and 1,4,8-trioxero-[4,6]-9-undecaneone were mixed in a round-bottom flask at a mass ratio of 4:1 under a nitrogen atmosphere to obtain a mixture. Sn(Oct)₂ dissolved in anhydrous toluene was then added to the mixture. The reaction was initially carried out at 60°C for 2 hours, and then heated to 115°C under a vacuum of 0.001 Pa for another 24 hours. The reaction mixture was cooled to room temperature and extracted with dichloromethane (DCM). The residue was then removed by centrifugation to obtain the prepolymer. Finally, the prepolymer was cast into a polytetrafluoroethylene mold and cured at 75°C after solvent removal to obtain a flexible polymer material.

[0045] Table 1: Performance test results of the self-healing flexible polymer material of the present invention

[0046]

[0047]

[0048] As can be seen from the experimental results in Table 1, the flexible polymer materials with self-healing properties prepared in Examples 1 to 5 have significantly improved tensile stress compared with the flexible polymer material prepared in Comparative Example 1.

[0049] This invention uses caprolactone and 1,4,8-trioxero-[4,6]-9-undecaneone as raw materials to prepare a prepolymer, which is then further reacted with a polyol prepared by this invention from epoxidized vegetable oil and (3-aminophenyl)boronic acid to prepare a flexible polymer material with self-healing properties. Compared with the flexible polymer material with self-healing properties prepared without the addition of the polyol of this invention, it can significantly increase the tensile stress; at the same time, it can also reduce the contact angle, which is beneficial to improving its biocompatibility.

[0050] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a flexible polymer material with self-healing properties, characterized in that, It includes the following steps: (1) Using caprolactone and 1,4,8-trioxerospiro-[4,6]-9-undecaneone as raw materials, a prepolymer was obtained by reaction under the action of a catalyst; (2) Take the prepolymer and react it with the polyol. After the reaction is completed, pour the reaction product into the mold and solidify it to obtain the flexible polymer material with self-healing properties. In step (1), the mass ratio of caprolactone to 1,4,8-trioxero-[4,6]-9-undecaneone is 3~5:1; The polyol in step (2) is prepared by the following method: Take epoxidized vegetable oil and (3-aminophenyl)boronic acid, and then heat them to react; after the reaction is complete, take the product to obtain the polyol. In step (2), the mass ratio of prepolymer to polyol is 75~95:25~5.

2. The method for preparing the flexible polymer material with self-healing properties according to claim 1, characterized in that, In step (1), the mass ratio of caprolactone to 1,4,8-trioxero-[4,6]-9-undecaneone is 4:

1.

3. The method for preparing the flexible polymer material with self-healing properties according to claim 1, characterized in that, The catalyst mentioned in step (1) is Sn(Oct)2.

4. The method for preparing the flexible polymer material with self-healing properties according to claim 1, characterized in that, In step (1), the mass of the catalyst used is 1 to 5% of the total mass of the raw materials caprolactone and 1,4,8-trioxero-[4,6]-9-undecaneone.

5. The method for preparing the flexible polymer material with self-healing properties according to claim 1, characterized in that, The reaction described in step (2) refers to the reaction at 65~75℃ for 1~3 hours.

6. The method for preparing the flexible polymer material with self-healing properties according to claim 1, characterized in that, The reaction described in step (2) refers to the reaction at 70°C for 2 hours.

7. The method for preparing the flexible polymer material with self-healing properties according to claim 1, characterized in that, The molar ratio of epoxidized vegetable oil to (3-aminophenyl)boronic acid is 1:1 to 1.

5.

8. The method for preparing the flexible polymer material with self-healing properties according to claim 1, characterized in that, The molar ratio of epoxidized vegetable oil to (3-aminophenyl)boronic acid is 1:1.

2.

9. The method for preparing the flexible polymer material with self-healing properties according to claim 1, characterized in that, The epoxidized vegetable oil is selected from one or more of epoxidized soybean oil, epoxidized corn oil, epoxidized rapeseed oil, epoxidized olive oil, and epoxidized flaxseed oil.

10. A flexible polymer material with self-healing properties prepared by the preparation method according to any one of claims 1 to 9.

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