A preparation method of self-repairing supramolecular reversible adhesion elastomer

Abstract

The present invention discloses a method for preparing a self-repairing supramolecular reversible adhesive elastomer, the method comprising the following steps: step 1, dissolving metal ions in a short-chain low-viscosity monofunctional acrylate; step 2, blending and stirring the solution dissolved in step 1 with a long-chain polyurethane acrylate to obtain an oligomer; step 3, blending and stirring the oligomer mixed in step 2 with a curing agent; step 4, using a syringe to slowly add an acrylate monomer containing a ligand to step 3, and slowly stirring during the addition of the ligand; step 5, adding an alkaline catalyst, placing it in a vacuum oven to remove bubbles, and curing it at room temperature to obtain an adhesive elastomer. The adhesive elastomer prepared by the method can adapt to various substrates and can be reversibly adhered at different temperatures.

Description

Technical Field

[0001] The invention relates to a method for preparing an elastomer adhesive, and in particular to a method for preparing a self-healing elastomer adhesive. Background Art

[0002] Supramolecular reversible adhesive elastomers are a new type of material, whose background technology is based on the interaction of non-covalent bonds. This material has become one of the research hotspots in the field of polymer science in recent years due to its unique dynamic reversibility, self-healing ability and responsiveness to the environment. These elastomers have attracted widespread attention due to their unique stimulus responsiveness, mild formation conditions and reversibility. Soft and tough supramolecular polymer adhesives can quickly adhere to different substrates and are essential for many fields, such as stretchable electronics, interfacial electrodes, drug delivery and biomedical devices. In nature, this controllable adhesion can be achieved through reversible non-covalent interactions, which can be manipulated by different stimuli, including special environments or secretions of organisms. Unlike plastic or resin-based hard adhesives, soft polymer adhesives can be deformed to cover cavities on the substrate and can eliminate mechanical stress. Introducing non-covalent interactions into the network as energy dissipation units is considered a powerful strategy for toughening elastomers. When these materials are stretched or loaded, the non-covalent interactions dissociate before the polymer chains break to dissipate a large amount of energy. Among various candidate designs, hydrogen bonding, metal-ligand coordination bonding, and π-π stacking, coordination bonds have higher bond energy and can endow elastomers with special properties, including self-healing ability, shape memory behavior, response to stimuli, and high dielectric constant. Therefore, in recent years, the synthesis of supramolecular elastomeric adhesives with coordination bonds as physical cross-linking bonds has received great attention. Summary of the invention

[0003] The purpose of the present invention is to provide a method for preparing a self-repairing supramolecular reversible adhesive elastomer. The adhesive elastomer prepared by the method can adapt to various different substrates and can reversibly adhere at different temperatures.

[0004] The objective of the present invention is achieved through the following technical solutions:

[0005] A method for preparing a self-repairing supramolecular reversible adhesion elastomer comprises the following steps:

[0006] Step 1: dissolve the metal ion in a short-chain low-viscosity monofunctional acrylate, and ultrasonicate for 10 to 30 minutes to fully dissolve it in the short-chain monofunctional acrylate, wherein: the metal ion is Cu 2+ 、Al 3+ 、Zn 2+ 、Zr 4+The short-chain low-viscosity monofunctional acrylate is one or two of butyl acrylate (BA), isooctyl acrylate (2-EHA), hydroxyethyl acrylate (HEA), and ethoxyethoxyethyl acrylate (EOEOA), which provide substrate flexibility and more flexible side groups and adhesion to the substrate;

[0007] Step 2: blending the solution obtained in step 1 with long-chain polyurethane acrylate, stirring for 30 to 60 minutes to obtain an oligomer, wherein the long-chain polyurethane acrylate is a difunctional oligomer with a viscosity of 400,000 Pa.s and a molecular weight of 8,000 to 12,000, which provides certain mechanical properties for the elastomer;

[0008] Step 3, blending the oligomers mixed in step 2 with a curing agent, stirring for 10 to 30 minutes, wherein the curing agent is one or two of 1,4-butanediol di(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), and pentaerythritol tetra(3-mercaptopropionate), and forming the adhesive into a three-dimensional network structure;

[0009] Step 4: slowly add the monomer containing the ligand into step 3 using a syringe, and slowly stir during the process of adding the ligand, wherein: the monomer containing the ligand is one of sodium vinyl sulfonate (VS), sodium 4-vinylbenzene sulfonate (NaSS), 3-sulfopropyl potassium acrylate (SPA) and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (DMAPS);

[0010] Step 5, adding an alkaline catalyst, placing in a vacuum oven to remove bubbles, and curing at room temperature to obtain an adhesive elastomer, wherein: the adhesive elastomer contains 0.5~5wt.% of metal ions, 3~15wt.% of short-chain low-viscosity monofunctional acrylates, 60~85wt.% of long-chain polyurethane acrylates, 10~35wt.% of a curing agent, and 0.5~5wt.% of a ligand-containing monomer; the alkaline catalyst is triethylamine, and the addition amount is 0.1~2wt.% of the adhesive elastomer; and the curing time is 4~24 hours.

[0011] Compared with the prior art, the present invention has the following advantages:

[0012] The present invention can form a polymer composite by simple solution processing at room temperature by mixing polymers with "complementary" supramolecular forces in a solution. The supramolecular reversible adhesion elastomer contains units based on non-covalent bond interactions. These interactions have natural reversibility, which enables the material to achieve structural reorganization under certain conditions and adapt to changes in the external environment, thereby maintaining performance stability under different application conditions. After a minor damage occurs, it can spontaneously repair through non-covalent bond interactions between molecules to restore its original performance. The imparting of self-healing ability significantly improves the service life and reliability of the material and reduces maintenance costs. The supramolecular elastomer has high adhesion strength to various substrates, which is mainly due to the non-covalent interaction between the abundant hydrogen bonding groups on the surface and the matrix. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 is the stress-strain curve of the elastomer of Example 1;

[0014] Figure 2 is the TG curve of the elastomer adhesive of Example 1;

[0015] Figure 3 This is an application diagram of elastomer adhesive. DETAILED DESCRIPTION

[0016] The technical solution of the present invention is further described below in conjunction with the accompanying drawings, but is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be included in the protection scope of the present invention.

[0017] Example 1

[0018] This embodiment provides a method for preparing a self-repairing supramolecular reversible adhesion elastomer, the method comprising the following steps:

[0019] Step 1: Cu 2+ Dissolve in hydroxyethyl acrylate and sonicate for 30 minutes to fully dissolve.

[0020] Step 2: Blend the solution obtained in step 1 with long-chain polyurethane acrylate having a molecular weight of 8000, and stir for 30 minutes.

[0021] Step 3: Blend the oligomers obtained in step 2 with trimethylolpropane tris(3-mercaptopropionate) and stir for 10 minutes.

[0022] Step 4: Use a syringe to slowly add sodium vinyl sulfonate (VS) into step 3, stirring slowly during the addition process.

[0023] Step 5: Add triethylamine, put into a vacuum oven to remove bubbles, and cure at room temperature for 24 hours to obtain an adhesive elastomer, wherein: the adhesive elastomer contains 1wt.% Cu 2+ , 10wt.% of hydroxyethyl acrylate, 60wt.% of polyurethane acrylate, 28wt.% of trimethylolpropane tris(3-mercaptopropionate), 1wt.% of sodium vinyl sulfonate (VS), and the amount of triethylamine added is 0.1wt.% of the adhesive elastomer.

[0024] The adhesive elastomer prepared in this embodiment has a self-healing efficiency of 80% at room temperature for 24 hours, a shear adhesion of 875KPa to an aluminum sheet at room temperature, and a peel adhesion toughness of 1000N / m. However, at -20°C, the shear strength is only 101Kpa, and the adhesion toughness is only 100N / m, which can achieve temperature-sensitive reversible adhesion. In addition, the mechanical properties of the elastomer can reach an elongation at break of nearly 1000% at a tensile rate of 400mm / min, a maximum tensile strength of 1.5Mpa, and an elastic modulus of 40Kpa.

[0025] Example 2

[0026] This embodiment provides a method for preparing a self-repairing supramolecular reversible adhesion elastomer, the method comprising the following steps:

[0027] Step 1: Zn 2+ Dissolve in hydroxyethyl acrylate and sonicate for 30 minutes to fully dissolve.

[0028] Step 2: Blend the solution obtained in step 1 with long-chain polyurethane acrylate having a molecular weight of 8000, and stir for 30 minutes.

[0029] Step 3: Blend the oligomers obtained in step 2 with trimethylolpropane tris(3-mercaptopropionate) and stir for 10 minutes.

[0030] Step 4: Use a syringe to slowly add sodium 4-vinylbenzenesulfonate (NaSS) into step 3, stirring slowly during the addition process.

[0031] Step 5: Add triethylamine, put into a vacuum oven to remove bubbles, and cure at room temperature for 24 hours to obtain an adhesive elastomer, wherein: the adhesive elastomer contains 3wt.% Zn 2+ , 5wt.% of hydroxyethyl acrylate, 70wt.% of polyurethane acrylate, 20wt.% of trimethylolpropane tris(3-mercaptopropionate), 2wt.% of sodium 4-vinylbenzenesulfonate (NaSS), and the amount of triethylamine added is 0.5wt.% of the adhesive elastomer.

[0032] Example 3

[0033] This embodiment provides a method for preparing a self-repairing supramolecular reversible adhesion elastomer, the method comprising the following steps:

[0034] Step 1: Zr 4+ Dissolve in butyl acrylate and sonicate for 30 minutes to fully dissolve.

[0035] Step 2: Blend the solution obtained in step 1 with long-chain polyurethane acrylate having a molecular weight of 10,000, and stir for 30 minutes.

[0036] Step 3: Blend the oligomers mixed in step 2 with 1,4-butanediol di(3-mercaptopropionate) and stir for 10 minutes.

[0037] Step 4: Use a syringe to slowly add 3-sulfopropyl potassium acrylate (SPA) into step 3, stirring slowly during the addition process.

[0038] Step 5: Add triethylamine, put into a vacuum oven to remove bubbles, and cure at room temperature for 24 hours to obtain an adhesive elastomer, wherein: the adhesive elastomer contains 2wt.% Zr 4+ , 15wt.% butyl acrylate, 65wt.% polyurethane acrylate, 15wt.% 1,4-butanediol di(3-mercaptopropionate), 3wt.% 3-sulfopropyl potassium acrylate (SPA), and the amount of triethylamine added is 2wt.% of the adhesive elastomer.

Claims

1. A method for preparing a self-repairing supramolecular reversible adhesion elastomer, characterized in that The method comprises the following steps: Step 1: dissolving the metal ion in a short-chain low-viscosity monofunctional acrylate, and subjecting it to ultrasonic treatment to fully dissolve it in the short-chain monofunctional acrylate, wherein: the metal ion is Cu 2+ 、Al 3+ 、Zn 2+ 、Zr 4+ The short-chain low-viscosity monofunctional acrylate is one or two of butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, and ethoxyethoxyethyl acrylate; Step 2: blending and stirring the solution obtained in step 1 with long-chain polyurethane acrylate to obtain an oligomer; Step 3, blending and stirring the oligomer mixed in step 2 with the curing agent; Step 4: slowly add the monomer containing the ligand into step 3 using a syringe, and slowly stir during the process of adding the ligand, wherein: the monomer containing the ligand is one of sodium vinyl sulfonate, sodium 4-vinylbenzene sulfonate, 3-sulfopropyl potassium acrylate and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide; Step 5, adding an alkaline catalyst, placing in a vacuum oven to remove bubbles, and curing at room temperature to obtain an adhesive elastomer, wherein: the adhesive elastomer contains 0.5~5wt.% of metal ions, 3~15wt.% of short-chain low-viscosity monofunctional acrylates, 60~85wt.% of long-chain polyurethane acrylates, 10~35wt.% of curing agents, and 0.5~5wt.% of ligand-containing monomers; the amount of the alkaline catalyst added is 0.1~2wt.% of the adhesive elastomer.

2. The method for preparing the self-repairing supramolecular reversible adhesion elastomer according to claim 1, characterized in that The ultrasonic treatment time is 10 to 30 minutes.

3. The method for preparing the self-repairing supramolecular reversible adhesion elastomer according to claim 1, characterized in that In the step 2, the stirring time is 30 to 60 minutes.

4. The method for preparing the self-repairing supramolecular reversible adhesion elastomer according to claim 1, characterized in that The molecular weight of the long-chain polyurethane acrylate is 8000-12000.

5. The method for preparing the self-repairing supramolecular reversible adhesion elastomer according to claim 1, characterized in that The curing agent is one or two of 1,4-butanediol di(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), and pentaerythritol tetra(3-mercaptopropionate).

6. The method for preparing the self-repairing supramolecular reversible adhesion elastomer according to claim 1, characterized in that The basic catalyst is triethylamine.

7. The method for preparing the self-repairing supramolecular reversible adhesion elastomer according to claim 1, characterized in that The curing time is 4 to 24 hours.

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