A high-temperature-resistant and organic-solvent-resistant supramolecular polymer adhesive and a preparation method thereof

Abstract

The application relates to a high-temperature-resistant and organic-solvent-resistant supramolecular polymer adhesive and a preparation method. The preparation method of the high-temperature-resistant and organic-solvent-resistant supramolecular polymer adhesive comprises the following steps: dissolving an inorganic salt in a solvent to obtain an inorganic salt solution, then adding a regulator and an organic ligand to obtain a polymer precursor solution; dissolving a dynamic covalent bond ligand in the solvent to obtain a dynamic covalent bond ligand solution; adding the polymer precursor solution into the dynamic covalent bond ligand solution to react, and drying to obtain the high-temperature-resistant and organic-solvent-resistant supramolecular polymer adhesive. Under the action of the regulator, the inorganic salt is first coordinated with the organic ligand, then the dynamic covalent bond ligand is added, and the high-temperature-resistant and organic-solvent-resistant supramolecular polymer adhesive with high strength and good dynamic reversibility is constructed in situ.

Description

Technical Field

[0001] This invention belongs to the field of adhesive preparation technology, specifically relating to a high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive and its preparation method. Background Technology

[0002] Adhesives are natural or synthetic substances that bond similar or dissimilar materials together. Natural adhesives, such as starch, fiber, and protein, have low bonding strength and a narrow range of applications. Synthetic adhesives, typically based on epoxy resins and cyanoacrylates, have drawbacks such as poor resistance to organic solvents and non-reusability. Currently, some adhesives on the market are reusable, but their weak cohesive energy results in weak adhesion; adhesives with strong cohesive energy are difficult to reuse.

[0003] Chinese patent application CN113061263A discloses a photocrosslinked dynamic reversible supramolecular polymer based on thioctic acid small molecule compounds. The preparation method of this photocrosslinked dynamic reversible supramolecular polymer adhesive includes the following steps: heating thioctic acid or a thioctic acid derivative to 70–200°C and stirring for 2–10 minutes to melt it; then adding a crosslinking agent and stirring for 2–10 minutes; finally adding a metal ion source and stirring for 2–10 minutes. The molar ratio of thioctic acid or a thioctic acid derivative, the crosslinking agent, and the metal ion source is 1:(0.01–1.5):(0.01–1), and the molar number of the metal ion source is based on the number of metal ions... Based on the molar amount, after the reaction is complete, heating is stopped, and 30-100 μL of the molten liquid is transferred to a substrate while still hot. This is then hot-pressed onto another substrate to obtain a thermal polymer with a thickness of 45-55 μm. The polymer is then irradiated with a UV-Vis light source with a wavelength of 300-450 nm for 20-60 minutes to obtain the photocrosslinked dynamic reversible supramolecular polymer adhesive based on thioctic acid small molecule compounds. The metal ion source consists of a metal inorganic salt and an organic solvent capable of dissolving the metal inorganic salt. The metal inorganic salt is at least one selected from ferric chloride, copper chloride, copper sulfate, zinc chloride, vanadium chloride, titanium chloride, cobalt chloride, and nickel chloride. The organic solvent is at least one selected from acetone, tetrahydrofuran, ethanol, or methanol. This photocrosslinked dynamic reversible supramolecular polymer adhesive based on thioctic acid small molecule compounds exhibits strong adhesion and can be reused, but it is not resistant to high temperatures or highly polar organic solvents. Summary of the Invention

[0004] The first objective of this invention is to provide a supramolecular polymer adhesive that is resistant to high temperatures and organic solvents to solve the technical problem that existing adhesives are difficult to simultaneously resist high temperatures and strong polar organic solvents.

[0005] The second objective of this invention is a method for preparing a high-temperature resistant and organic solvent resistant supramolecular polymer adhesive.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a high-temperature resistant and organic solvent resistant supramolecular polymer adhesive includes the following steps: dissolving an inorganic salt in a solvent, then adding a modifier and an organic ligand to obtain a polymer precursor solution; dissolving a dynamic covalent ligand in the solvent to obtain a dynamic covalent ligand solution; adding the polymer precursor solution to the dynamic covalent ligand solution for reaction, and drying to obtain the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive.

[0008] Furthermore, the dynamic covalent ligand is one or more of cinnamic acid, 9-anthracarboxylic acid, and thioctic acid.

[0009] Furthermore, the molar ratio of the inorganic salt, regulator, organic ligand, and dynamic covalent ligand is 1:1:0.5-2:1-100; the molar concentration of the inorganic salt solution is 0.015-0.017 mol / L; and the molar concentration of the dynamic covalent ligand solution is 0.015-1.5 mol / L.

[0010] Furthermore, the inorganic salt is one or more of calcium carbonate, magnesium nitrate, aluminum sulfate, zirconium chloride, ferric nitrate, and copper nitrate; the regulator is one or more of triethanolamine, tetraethylethylenediamine, and triethylamine; and the organic ligand is terephthalic acid.

[0011] Furthermore, the solvent is one or more of anhydrous ethanol, methanol, and N,N-dimethylformamide.

[0012] Furthermore, the inorganic salt is dissolved in the solvent and ultrasonically dispersed to obtain the inorganic salt solution, then the regulator and organic ligand are added and ultrasonically dispersed to obtain the polymer precursor solution; the dynamic covalent ligand is dissolved in the solvent and ultrasonically dispersed to obtain the dynamic covalent ligand solution.

[0013] Furthermore, the polymer precursor solution is added dropwise to the dynamic covalent ligand solution, reacted at room temperature for 4-24 hours, and the precipitate is obtained after filtration. The precipitate is then dried at 20-40°C to obtain the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive.

[0014] Furthermore, the vacuum degree of the filtration is 0.05-0.08 MPa.

[0015] A high-temperature resistant and organic solvent resistant supramolecular polymer adhesive is prepared by the above-described preparation method for a high-temperature resistant and organic solvent resistant supramolecular polymer adhesive.

[0016] The beneficial effects of this invention are:

[0017] The dynamic covalent ligands used in this invention combine the high stability of covalent bonds with the dynamic reversibility of non-covalent bonds, enabling the reusable high-temperature and organic solvent-resistant supramolecular polymer adhesive of this invention. By adding modifiers to regulate the dynamic covalent bonds and organic ligands, the adhesive strength of the high-temperature and organic solvent-resistant supramolecular polymer adhesive of this invention is increased. The inorganic salts of this invention, after coordination with organic ligands, can withstand highly polar organic solvents, thus also giving the adhesive solvent resistance.

[0018] The inorganic salt of the present invention first coordinates with an organic ligand under the action of a regulator, and then a dynamic covalent ligand is added to construct a high-strength supramolecular polymer adhesive with good dynamic reversibility, high temperature resistance, and organic solvent resistance in situ.

[0019] The high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of this invention is a semi-transparent elastomer that is easy to store. The preparation method of this invention is simple, requiring no heating, pressurization, or irradiation with a specific wavelength light source; it can be obtained by stirring at room temperature, thus saving energy.

[0020] The high-temperature resistant and organic solvent resistant supramolecular polymer adhesive of the present invention has strong resistance to highly polar organic solvents, exhibits strong adhesion at both low and high temperatures, and maintains high adhesion strength even after multiple cycles. Attached Figure Description

[0021] Figure 1 The infrared spectra of the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive, cinnamic acid, and polymer precursor solution of Example 1 are shown.

[0022] Figure 2 The XRD patterns are of the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive and polymer precursor solution of Example 1.

[0023] Figure 3 The DSC diagram of the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive of Example 1 is shown below.

[0024] Figure 4 This is a SEM image of the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive of Example 1;

[0025] Figure 5 The rheological test diagram shows the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive of Example 1.

[0026] Figure 6 The adhesion force diagram of the iron sheet after immersion in dimethyl sulfoxide for 30 days in the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive of Example 1. Detailed Implementation

[0027] The present invention will be further described below with reference to the embodiments and accompanying drawings.

[0028] Example 1

[0029] The preparation method of the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive in Example 1 includes the following steps: Zirconia chloride is dissolved in anhydrous ethanol and ultrasonically dispersed to obtain a zirconium chloride solution. Triethylamine and terephthalic acid are added and ultrasonically dispersed to obtain a polymer precursor solution. Cinnamic acid is dissolved in anhydrous ethanol and ultrasonically dispersed to obtain a cinnamic acid solution. The polymer precursor solution is added dropwise to the dynamic covalent ligand solution. The reaction is stirred at room temperature for 12 hours. The supernatant is then removed by filtration under a vacuum of 0.05 MPa to obtain a precipitate. The precipitate is dried in a vacuum drying oven at 30°C for 24 hours to obtain the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive. The molar ratio of zirconium chloride, triethylamine, terephthalic acid, and cinnamic acid is 1:1:1:50. The molar concentration of the zirconium chloride solution is 0.015 mol / L, and the molar concentration of the cinnamic acid solution is 0.75 mol / L.

[0030] Examples 2-18, Comparative Examples 1-6

[0031] The preparation methods of the high-temperature resistant and organic solvent resistant supramolecular polymer adhesives of Examples 2-18 and Comparative Examples 1-6 are largely the same as those of Example 1. The difference between the preparation methods of the high-temperature resistant and organic solvent resistant supramolecular polymer adhesives of Examples 2-18 and Comparative Examples 1-6 and Example 1 is that the inorganic salts and dynamic covalent ligands used in Examples 2-18 and Comparative Examples 1-6 are different from those in Example 1. The inorganic salts and dynamic covalent ligands used in Examples 2-18 and Comparative Examples 1-6 are shown in Table 1.

[0032] Table 1 Inorganic salts and dynamically covalently bonded ligands in Examples 2-24

[0033]

[0034]

[0035] from Figure 1 and Figure 2 As can be seen from the data, the infrared peak of the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of Example 1 is at 3122 cm⁻¹. -1 1639cm -1 The characteristic peak of cinnamic acid is present at 752 cm⁻¹. -1The characteristic peak of zirconium chloride is present at 1380 cm⁻¹. -1 1583cm -1 The presence of characteristic peaks for terephthalic acid indicates the successful synthesis of the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of Example 1. Figure 2 and Figure 3 It can be seen that both the polymer precursor solution and the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive of Example 1 are amorphous. The glass transition temperature of the organic solvent resistant supramolecular polymer adhesive of Example 1 is 102°C. This is because inorganic salts have high melting points, and adding inorganic salts will increase the glass transition temperature of the organic solvent resistant supramolecular polymer adhesive of the present invention. The higher the glass transition temperature, the better the high-temperature resistance. Figure 4 It can be seen that the polymer precursor solution and the high-temperature resistant, organic solvent-resistant supramolecular polymer binder in Example 1 are formed by the crosslinking of spherical particles. Figure 5 As can be seen from point a, the storage modulus G' is significantly greater than the loss modulus G", indicating that elasticity dominates in this fluid. Figure 5 As can be seen from b, the complex viscosity decreases with increasing angular frequency. The better the heat resistance of the adhesive, the greater its complex viscosity and the more pronounced its shear thinning behavior. Figure 5 As can be seen from c, the storage modulus and loss modulus gradually decrease with increasing temperature. This is because at high temperatures, molecular vibrations intensify, leading to a more loose internal structure in the material, thus reducing the storage modulus and loss modulus. From Figure 5 The viscoelasticity test results under temperature cycling at 25-100℃ show that the viscosity remains basically unchanged as the number of cycles increases.

[0036] Experimental Example 1

[0037] Adhesion performance test

[0038] The adhesion performance of the high-temperature and organic solvent resistant supramolecular polymer adhesive of Example 1 to iron blocks was tested under different temperatures and humidity conditions. The test results are shown in Tables 2 and 3.

[0039] Table 2 shows the adhesion properties of the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of Example 1 to iron blocks at different temperatures.

[0040]

[0041] Table 3 shows the adhesion performance of the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of Example 1 to iron blocks under different humidity levels.

[0042]

[0043] As can be seen from Tables 2 and 3, the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of Example 1 still exhibits strong adhesion properties in high humidity environments, at -20°C, and at 100°C. This is because the high-melting-point inorganic salt enhances the adhesive's high-temperature resistance, and the coordination bonds remain stable within a certain temperature range and under high humidity conditions. Therefore, the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of this invention also maintains stability under these conditions.

[0044] Experiment Example 2

[0045] Cyclic performance test

[0046] The high-temperature resistant and organic solvent resistant supramolecular polymer adhesive of Example 1 was re-adheded between two iron blocks and two pieces of glass after a tensile test. The high-temperature resistant and organic solvent resistant supramolecular polymer adhesive of Example 1 was melted at 130°C and then cured at room temperature for 20 minutes. The adhesive strength was measured using a tensile tester. The test results are shown in Table 4.

[0047] Table 4 shows the adhesion strength of the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive to iron blocks and glass cycles in Example 1.

[0048]

[0049] As can be seen from Table 4, the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive of Example 1 still has a large adhesion strength after 5 high-temperature cycles.

[0050] Experimental Example 3

[0051] Polar solvent resistance test

[0052] The adhesion properties of the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of Example 1 were tested in chloroform, tetrahydrofuran, acetonitrile, ethanol, and dimethyl sulfoxide. The material, with an iron block as a substrate, was well-adheded and then immersed in a highly polar organic solvent for 30 days. After immersion, the material was removed and its adhesion strength was tested using a tensile tester. The test results are shown in Table 5.

[0053] Table 5. Adhesion performance of the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of Example 1 in polar organic solvents.

[0054]

[0055] As can be seen from Table 5, the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of Example 1 has good resistance to strong polar organic solvents. It has high adhesion strength in strong polar organic solvents such as chloroform, tetrahydrofuran, acetonitrile, ethanol and dimethyl sulfoxide. This is because, after coordination with ligands, the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of the present invention has a structure similar to MOFs. The stable coordination bonds make the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive of the present invention insoluble in strong polar organic solvents, thereby enabling it to resist strong polar organic solvents.

Claims

1. A method for preparing a high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive, characterized in that, Includes the following steps: Inorganic salts are dissolved in a solvent to obtain an inorganic salt solution, and then a regulator and an organic ligand are added to obtain a polymer precursor solution. The dynamic covalent ligand is dissolved in the solvent to obtain a dynamic covalent ligand solution; The polymer precursor solution is added to the dynamic covalent ligand solution for reaction, and after drying, the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive is obtained. The dynamic covalent ligand is one or more of cinnamic acid, 9-anthracarboxylic acid, and lipoic acid. The molar ratio of the inorganic salt, regulator, organic ligand, and dynamic covalent ligand is 1:1:0.5-2:1-100. The molar concentration of the inorganic salt solution is 0.015-0.017 mol / L. The molar concentration of the dynamic covalent ligand solution is 0.015-1.5 mol / L. The inorganic salt is one or more of calcium carbonate, magnesium nitrate, aluminum sulfate, zirconium chloride, ferric nitrate, and copper nitrate. The regulator is one or more of triethanolamine, tetraethylethylenediamine, and triethylamine. The organic ligand is terephthalic acid.

2. The method for preparing the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive according to claim 1, characterized in that, The solvent is one or more of anhydrous ethanol, methanol, and N,N-dimethylformamide.

3. The method for preparing the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive according to claim 1, characterized in that, The inorganic salt is dissolved in the solvent and dispersed uniformly by ultrasonication to obtain the inorganic salt solution. Then, the regulator and organic ligand are added and dispersed by ultrasonication to obtain the polymer precursor solution. The dynamic covalent ligand is dissolved in the solvent and dispersed uniformly by ultrasonication to obtain the dynamic covalent ligand solution.

4. The method for preparing the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive according to claim 1 or 3, characterized in that, The polymer precursor solution is added dropwise to the dynamic covalent ligand solution, and the reaction is carried out at room temperature for 4-24 h. After filtration, a precipitate is obtained, and the precipitate is dried at 20-40 °C to obtain the high-temperature resistant and organic solvent resistant supramolecular polymer adhesive.

5. The method for preparing the high-temperature resistant and organic solvent-resistant supramolecular polymer adhesive according to claim 4, characterized in that, The vacuum degree of the filtration is 0.05-0.08 MPa.

6. A supramolecular polymer adhesive resistant to high temperature and organic solvents, characterized in that, It is prepared by the method for preparing high-temperature resistant and organic solvent resistant supramolecular polymer adhesive according to any one of claims 1-5.

Images