A self -repairing and recyclable polyurethane polymer polyetric polymer and its preparation methods and applications

Abstract

The invention discloses an intrinsic self-repairing recoverable polyurethane polymer. The intrinsic self-repairing recoverable polyurethane polymer comprises, by weight, 0.6-1.8 parts of an arylpinacol structure-containing diol monomer, 2.5-22.5 parts of a polyester or polyether diol monomer, 0.5-2.0 parts of a polyisocyanate monomer, 0.6-2.0 parts of a diisocyanate monomer and 0.1-0.6 parts of a polyol or polymercaptan monomer cross-linking agent. The invention also provides a preparation method of the polyurethane polymer and an application of the polyurethane polymer. The polyurethane polymer can realize self-repairing and recycling, and the self-repairing and recovering mechanism is characterized in that reversible C-C advanced cleavage of the arylpinacol center in the molecular chain of the polymer and diffusion, penetration and entanglement of the interface molecule chain make a thermal-reversible reaction occur in the molecule level in order to macromolecular chains of the damaged surface or among broken particles of the polymer and realize self-repairing and solid recovery, so prolongation of the service life of the polymer material, energy saving and resource waste reduction are facilitated, and the development trend of the global low carbon economy is met.

Description

technical field

[0001] The invention belongs to the technical field of intelligent polymer materials, and more specifically relates to an intrinsic self-healing and recyclable polyurethane polymer and its preparation method and application. Background technique

[0002] Polymers and their composite materials have the advantages of high specific strength and specific modulus, excellent fatigue resistance, good shock absorption, high overload safety performance, convenient molding, corrosion resistance, excellent electrical insulation performance, etc., overcoming traditional metal and inorganic materials. The limitations of non-metals are widely used in many fields. However, during processing and use, polymer materials will inevitably produce defects such as microcracks, which will easily lead to a decrease in material stability, shorten its service life, and even cause safety hazards. How to improve the service life and stability of polymer materials and achieve high perfor...

Examples

Embodiment 1

[0065] Add 8.0 parts of 4-hydroxybenzophenone into a 150ml three-neck flask with magnetic stirring, add 40 parts of DMF solvent and stir to dissolve, then add 7.4 parts of 2-bromoethanol dropwise at a uniform speed, and then add 12 parts of anhydrous Potassium carbonate was heated to 90°C for 18 hours under nitrogen atmosphere. After the reaction, the mixed solution was filtered to remove the precipitate, poured into distilled water and adjusted to pH = 7, suction filtered and freeze-dried to obtain a white solid of 4-hydroxyethylbenzophenone, the molecular structure of which was shown below. The H NMR and IR spectra of the molecule are shown in figure 2 , 3 .

[0066]

Embodiment 2

[0068] Add 10ml of DMF solution with 5.0 parts of 4-hydroxyethyl benzophenone and 0.2 parts of glacial acetic acid in DMF solution into a quartz colorimetric tube, then add 30.0 parts of isopropanol, and react under a 315nm ultraviolet lamp 6d. After the reaction, the mixed solution was poured into distilled water to precipitate, filtered with suction and freeze-dried to obtain a white powder. Purified by silica gel chromatography, the eluent is petroleum ether / ethyl acetate=1:1 (v / v), the corresponding eluate is collected and the solvent is evaporated under reduced pressure to obtain 1,2-bis(4-(2-hydroxy Ethoxy)phenyl)-1,2-diphenylethane-1,2-diol, the molecular structure is as follows. The H NMR and IR spectra of the molecule are shown in Figure 4 , 5 .

[0069]

Embodiment 3

[0071] Under an argon atmosphere, add 5.0 parts of polytetrahydrofuran PTMEG1000 (number-average molecular weight: 1000) into a 250ml three-necked flask with mechanical stirring, heat up to 60°C to melt PTMEG1000, add 100.0 parts of DMF solvent, 1.1 parts of six sub- Methyl diisocyanate trimer, 1.3 parts of hexamethylene diisocyanate monomer and 0.005 part of dibutyltin dilaurate catalyst, add 1.2 parts of compound obtained by embodiment 2 after reacting 5h at 60 ℃ (due to the benzene ring Steric hindrance, the activity of the hydroxyl group on the C-C bond in the center of aromatic pinacol is very weak, and basically does not participate in the reaction, and the two primary hydroxyl groups at the end actually participate in the polymerization), after reacting at room temperature for 24 hours, add 0.25 parts of triethanolamine to continue the reaction After 12 hours, the cross-linked polyurethane containing aromatic pinacol structure was obtained by precipitation in methanol so...

technical field

[0001] The invention belongs to the technical field of intelligent polymer materials, and more specifically relates to an intrinsic self-healing and recyclable polyurethane polymer and its preparation method and application. Background technique

[0002] Polymers and their composite materials have the advantages of high specific strength and specific modulus, excellent fatigue resistance, good shock absorption, high overload safety performance, convenient molding, corrosion resistance, excellent electrical insulation performance, etc., overcoming traditional metal and inorganic materials. The limitations of non-metals are widely used in many fields. However, during processing and use, polymer materials will inevitably produce defects such as microcracks, which will easily lead to a decrease in material stability, shorten its service life, and even cause safety hazards. How to improve the service life and stability of polymer materials and achieve high perfor...

Examples

Embodiment 1

[0065] Add 8.0 parts of 4-hydroxybenzophenone into a 150ml three-neck flask with magnetic stirring, add 40 parts of DMF solvent and stir to dissolve, then add 7.4 parts of 2-bromoethanol dropwise at a uniform speed, and then add 12 parts of anhydrous Potassium carbonate was heated to 90°C for 18 hours under nitrogen atmosphere. After the reaction, the mixed solution was filtered to remove the precipitate, poured into distilled water and adjusted to pH = 7, suction filtered and freeze-dried to obtain a white solid of 4-hydroxyethylbenzophenone, the molecular structure of which was shown below. The H NMR and IR spectra of the molecule are shown in figure 2 , 3 .

[0066]

Embodiment 2

[0068] Add 10ml of DMF solution with 5.0 parts of 4-hydroxyethyl benzophenone and 0.2 parts of glacial acetic acid in DMF solution into a quartz colorimetric tube, then add 30.0 parts of isopropanol, and react under a 315nm ultraviolet lamp 6d. After the reaction, the mixed solution was poured into distilled water to precipitate, filtered with suction and freeze-dried to obtain a white powder. Purified by silica gel chromatography, the eluent is petroleum ether / ethyl acetate=1:1 (v / v), the corresponding eluate is collected and the solvent is evaporated under reduced pressure to obtain 1,2-bis(4-(2-hydroxy Ethoxy)phenyl)-1,2-diphenylethane-1,2-diol, the molecular structure is as follows. The H NMR and IR spectra of the molecule are shown in Figure 4 , 5 .

[0069]

Embodiment 3

[0071] Under an argon atmosphere, add 5.0 parts of polytetrahydrofuran PTMEG1000 (number-average molecular weight: 1000) into a 250ml three-necked flask with mechanical stirring, heat up to 60°C to melt PTMEG1000, add 100.0 parts of DMF solvent, 1.1 parts of six sub- Methyl diisocyanate trimer, 1.3 parts of hexamethylene diisocyanate monomer and 0.005 part of dibutyltin dilaurate catalyst, add 1.2 parts of compound obtained by embodiment 2 after reacting 5h at 60 ℃ (due to the benzene ring Steric hindrance, the activity of the hydroxyl group on the C-C bond in the center of aromatic pinacol is very weak, and basically does not participate in the reaction, and the two primary hydroxyl groups at the end actually participate in the polymerization), after reacting at room temperature for 24 hours, add 0.25 parts of triethanolamine to continue the reaction After 12 hours, the cross-linked polyurethane containing aromatic pinacol structure was obtained by precipitation in methanol so...

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