Biomass wet adhesion physical adhesive and preparation method thereof
By preparing biomass wet adhesion physical adhesives, the mechanical properties and swelling problems of PAA and PEI composite hydrogels were solved, high-strength adhesion and biocompatibility were achieved, making them suitable for applications such as cultural relics restoration.
Patent Information
- Application Number
- CN202510781509.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-12
- Publication Date
- 2025-09-26
AI Technical Summary
The existing wet adhesion hydrogels formed by the composite of PAA and PEI have insufficient mechanical properties and swelling problems in practical applications, making it difficult to meet high strength requirements and complex mechanical challenges.
PAA and DA were first mixed, and then PEI was added to form mixture B. The mixture was centrifuged at 10,000 rpm for 30 minutes to prepare a biomass wet adhesion physical adhesive. DA was used to form a polydopamine coating on the hydrogel surface and increase the number of hydrogen bonds, thereby enhancing the cross-linking density.
It improves the mechanical properties and wet adhesion properties of the adhesive, maintains structural integrity, has excellent biocompatibility and safety, does not contain toxic gases, and is suitable for fields such as cultural relics restoration.
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of adhesive synthesis, and in particular relates to a biomass wet-adhesive physical adhesive and a preparation method thereof. Background Art
[0002] Adhesives are substances that can tightly bond two or more materials through adhesion. They are characterized by ease of operation, wide application, rapid curing, and high bond strength. Adhesives play an important role in many fields. Adhesives have good flowability and can form a uniform adhesive layer between irregular surfaces, providing reliable adhesion. Cyanoacrylate and formaldehyde adhesives are commonly used organic solvent adhesives, but cyanoacrylate does not perform well on damp substrates. Formaldehyde adhesives can release formaldehyde in certain situations, which greatly limits their application.
[0003] Therefore, scientists invented adhesives with polyacrylic acid (PAA) and polyethyleneimine (PEI) as components. However, the wet adhesive hydrogel formed by the composite of PAA and PEI has some shortcomings in practical applications: First, the most obvious point is that the PAA-PEI hydrogel will swell after absorbing water, which is its inherent property as a hydrogel. Although this swelling behavior helps it to form close contact on the wet tissue surface, it may also cause it to gradually lose its shape and adhesion in a physiological environment; secondly, although the composite of PAA and PEI can improve the adhesion properties of the hydrogel, in some application scenarios with high strength requirements, its adhesion strength may still not be enough to meet the requirements; thirdly, the mechanical properties of the PAA-PEI hydrogel may not be sufficient when facing complex mechanical challenges. For example, when the tissue surface is irregular or there is excessive mechanical pressure, its adhesion performance may be affected. Summary of the Invention
[0004] One object of the present invention is to provide a method for preparing a biomass wet-adhesive physical adhesive, which effectively solves the problem of insufficient mechanical properties of wet-adhesive hydrogels formed by the composite of PAA and PEI in practical applications.
[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is:
[0006] A method for preparing a biomass wet-adhesive physical adhesive comprises the following steps:
[0007] S1. PAA with a mass concentration of 50%, deionized water and DA were mixed, and then ultrasonicated at 50°C for 10 min to obtain a mixture A.
[0008] The mass ratio of DA to PAA is 1% to 3%, and the ratio of PAA to deionized water is 1 g: 0 to 3.02 mL.
[0009] S2. Add PEI with a mass concentration of 30% to mixture A, and stir to obtain mixture B.
[0010] The mass ratio of PEI to PAA is 0.5 to 1.5.
[0011] S3. Centrifuge the mixture B at 10,000 rpm for 30 minutes, discard the supernatant, and obtain a biomass wet adhesion physical adhesive.
[0012] Another object of the present invention is to provide a biomass wet adhesion physical adhesive prepared using the preparation method described in the above embodiment.
[0013] Another object of the present invention is to provide a use of the biomass wet adhesion physical adhesive described in the above embodiment, and to apply it to the restoration of cultural relics.
[0014] Compared with the prior art, the beneficial technical effects of the present invention are:
[0015] The biomass wet-adhesive physical adhesive prepared by the present invention has excellent biocompatibility, mechanical properties and wet-adhesive properties. The raw materials of the present invention are low-cost, no organic solvents are used, and the present invention is safer than the existing technology and does not produce toxic gases. DETAILED DESCRIPTION
[0016] The relevant terms of the present invention are explained as follows:
[0017] (1) DA is dopamine hydrochloride, a catecholamine neurotransmitter containing o-diphenolic hydroxyl groups and amino groups. It is a metabolic intermediate of tyrosine and has good biological activity. In materials science, DA can be oxidatively polymerized to form polydopamine (PDA), which has good hydrophilicity and adhesion. PDA can form complexes with a variety of materials to improve the surface properties of the materials.
[0018] (2) PEI is polyethyleneimine, which is a cationic polymer containing a large number of amino groups and has good water solubility, biocompatibility and gene transfection ability.
[0019] (3) PAA is polyacrylic acid, which is an anionic polymer with a large number of carboxyl groups and has excellent water solubility and biocompatibility.
[0020] Example 1: A method for preparing a biomass wet adhesion physical adhesive, comprising the following steps:
[0021] S1. PAA with a mass concentration of 50%, deionized water and DA were mixed, and then ultrasonicated at 50°C for 10 min to obtain a mixture A.
[0022] In this embodiment, the mass of PAA is 0.3 g, the mass of DA is 0.003 g, and the volume of deionized water is 0.006 mL to 0.906 mL.
[0023] S2. Take 1 ml of PEI with a mass concentration of 30% and add it to mixture A, stir to obtain mixture B.
[0024] In this embodiment, the mass ratio of PEI to PAA is 0.5-1.5.
[0025] S3. Centrifuge the mixture B at 10,000 rpm for 30 minutes, discard the supernatant, and obtain the biomass wet adhesion physical adhesive, which is then placed in a sealed container for storage.
[0026] Example 2: A method for preparing a biomass wet adhesion physical adhesive, comprising the following steps:
[0027] S1. PAA with a mass concentration of 50%, deionized water and DA were mixed, and then ultrasonicated at 50°C for 10 min to obtain a mixture A.
[0028] In this embodiment, the mass of PAA is 0.3 g, the mass of DA is 0.006 g, and the volume of deionized water is 0.003 mL to 0.903 mL.
[0029] S2. Take 1 ml of PEI with a mass concentration of 30% and add it to mixture A, stir to obtain mixture B.
[0030] In this embodiment, the mass ratio of PEI to PAA is 0.5-1.5.
[0031] S3. Centrifuge the mixture B at 10,000 rpm for 30 minutes, discard the supernatant, and obtain the biomass wet adhesion physical adhesive, which is then placed in a sealed container for storage.
[0032] Example 3: A method for preparing a biomass wet adhesion physical adhesive, comprising the following steps:
[0033] S1. PAA with a mass concentration of 50%, deionized water and DA were mixed, and then ultrasonicated at 50°C for 10 min to obtain a mixture A.
[0034] In this embodiment, the mass of PAA is 0.3 g, the mass of DA is 0.009 g, and the volume of deionized water is 0 mL to 0.9 mL.
[0035] S2. Take 1 ml of PEI with a mass concentration of 30% and add it to mixture A, stir to obtain mixture B.
[0036] In this embodiment, the mass ratio of PEI to PAA is 0.5-1.5.
[0037] S3. Centrifuge the mixture B at 10,000 rpm for 30 minutes, discard the supernatant, and obtain the biomass wet adhesion physical adhesive, which is then placed in a sealed container for storage.
[0038] The PEI and PAA used in Examples 1-3 were both produced by Shanghai MacLean Biochemical Technology Co., Ltd., and DA was produced by Anaiji Chemical.
[0039] The applicant's research has discovered that mixing PEI and DA first accelerates DA oxidation, forming an oxide film on the colloid surface. Therefore, the present invention first mixes PAA and DA before adding PEI. In step S3, the centrifugation duration and speed can affect the colloid's curing time. Without centrifugation, Mixture B solidifies in approximately two hours. However, after centrifugation, the curing time is shortened to approximately one hour, significantly improving preparation efficiency.
[0040] Example 4: A biomass wet-adhesive physical adhesive is prepared using any of the preparation methods in Examples 1 to 3. The biomass wet-adhesive physical adhesive of this example has excellent biocompatibility, mechanical properties, and wet-adhesive properties.
[0041] The biomass wet-adhesive physical adhesive provided in this embodiment has great potential for application in the field of cultural relic restoration. Currently, the adhesive commonly used in cultural relic restoration is cyanovinyl ester adhesive, which is toxic and has shortcomings such as poor stability, heat resistance, and incompatibility with humid environments, which limit its scope of application. The biomass wet-adhesive physical adhesive provided in this embodiment has the advantages of wet adhesion, oxidation resistance, good chemical stability, and good biocompatibility. Furthermore, it does not contain any volatile components and will not cause any damage to the user during use, thus having broad application prospects.
[0042] The present invention is based on the fact that PAA and PEI carry a large amount of charge, which can form strong electrostatic interactions with charged substances on the substrate surface. The introduction of DA, which has wet adhesion properties, synergistically enhances the wet adhesion of the adhesive. DA forms a polydopamine coating on the hydrogel surface, and its introduction increases the number of hydrogen bonds in the hydrogel, thereby enhancing the hydrogel's adhesion properties. DA, through its catechol structure, forms covalent bonds or hydrogen bonds with PAA and PEI in the hydrogel, thereby increasing the hydrogel's crosslinking density. This crosslinking action limits excessive swelling of the hydrogel, allowing it to maintain a certain level of structural integrity after absorbing water, thereby improving the mechanical properties of the hydrogel caused by swelling. DA is an important neurotransmitter with excellent biological activity, and its biological activity helps improve the cytocompatibility of the composite material and reduce cytotoxicity. Therefore, the introduction of DA enhances the crosslinking degree, adhesion, mechanical properties, and biocompatibility of the hydrogel.
[0043] In some other embodiments, DA in step S1 can also be replaced by tannic acid or gallic acid. Since both tannic acid and gallic acid contain a large number of phenolic hydroxyl groups in their chemical structures, they can form a large number of hydrogen bonds or covalent bonds with the carboxyl and amino groups on the PEI and PAA polymer chains, thereby enhancing the cross-linking density of the hydrogel.
[0044] The present invention has a simple preparation process, low-cost raw materials, and avoids the use of organic solvents. Therefore, the biomass wet-adhesive physical adhesive prepared by the present invention is safer than existing cyanoacrylate and formaldehyde adhesives and does not produce toxic gases.
[0045] Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or substitutions made by technicians in this technical field within the essential scope of the present invention should also fall within the scope of protection of the present invention.
Claims
1. A method for preparing a biomass wet adhesion physical adhesive, characterized in that: The following steps are involved: S1. PAA with a mass concentration of 50%, deionized water, and DA were mixed and ultrasonicated at 50°C for 10 min to obtain a mixture A. The mass ratio of DA to PAA is 1% to 3%, and the ratio of PAA to deionized water is 1 g: 0 to 3.02 mL; S2. Add PEI with a mass concentration of 30% to mixture A and stir to obtain mixture B; The mass ratio of PEI to PAA is 0.5 to 1.5; S3. Centrifuge the mixture B and discard the supernatant to obtain a biomass wet adhesion physical adhesive.
2. The method for preparing the biomass wet adhesion physical adhesive according to claim 1, characterized in that: In step S3, the centrifugation condition is 10000 rpm for 30 min.
3. A biomass wet adhesion physical adhesive, characterized in that: The preparation method is as described in claim 1 or claim 2.
4. A use of a biomass wet adhesion physical adhesive, characterized in that: The biomass wet adhesion physical adhesive is prepared by the preparation method according to claim 1 or claim 2, and is used for restoration of cultural relics.