Underwater adhesive based on biomimetic mineralization organic-inorganic hybridization as well as preparation method and application of underwater adhesive

Abstract

The invention discloses an underwater adhesive based on biomimetic mineralization organic-inorganic hybridization as well as a preparation method and application thereof, and belongs to the technical field of adhesives. The adhesive comprises unsaturated grease, an inorganic compound and an oxidizing agent. The adhesive disclosed by the invention has high bonding strength for various base materials, and keeps relatively high strength in various solution environments. The adhesive provided by the invention can be used for cementing, maintenance and reinforcement of underwater structures. The selected raw materials are low in cost and easy to obtain, the preparation process is simple, complex synthesis is not needed, and the adhesive is suitable for industrial large-scale production and has a profound application prospect in the technical field of adhesives.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and particularly relates to an underwater adhesive based on biomimetic mineralized organic-inorganic hybridization, a preparation method thereof, and an application thereof. Background Art

[0002] Underwater adhesives have received extensive attention due to their application prospects in the fields of biomedicine, ocean engineering, underwater repair, etc. Existing adhesives can achieve firm bonding on dry surfaces, but often exhibit poor bonding performance or even bonding failure in humid or underwater environments. This is mainly because: on the one hand, the hydration layer formed at the bonding interface hinders the full contact and close interaction between the adhesive and the substrate; on the other hand, the adhesive body undergoes swelling and degradation due to the destructive effect of water molecules, ultimately leading to a significant decline in bonding performance. Therefore, developing new high-strength and stable underwater adhesives has important research significance and application value.

[0003] In recent years, inspired by the underwater adhesion of marine organisms such as mussels, barnacles, and sabellid worms, researchers have successfully developed a series of biomimetic underwater adhesion systems based on catechol action, polyelectrolyte complexation, and supramolecular assembly. However, most of these modification strategies have problems such as high preparation cost, cumbersome operation methods, poor system stability, or long curing time, which greatly limit their industrial development. Therefore, although significant progress has been made in the research of underwater adhesives, achieving high-strength, stable, and scalable underwater adhesives remains a huge challenge. Summary of the Invention

[0004] Different from the bioadhesion systems mainly composed of organic substances such as mussels and barnacles, oyster adhesive is an organic-inorganic hybrid system based on biomineralization, in which the organic component serves as the adhesive soft phase and the inorganic component serves as the reinforcing hard phase. Through the complementary advantages and synergistic optimization of the organic phase and the inorganic phase, strong and stable underwater bonding is successfully achieved. Therefore, imitating the oyster mineralization wet adhesion mechanism can provide new ideas for the design and development of high-performance underwater adhesives.

[0005] To solve the deficiencies in the prior art, the present invention provides an underwater adhesive based on biomimetic mineralized organic-inorganic hybridization, a preparation method thereof, and an application thereof.

[0006] The underwater adhesive composition based on biomimetic mineralized organic-inorganic hybridization provided by the present invention includes: unsaturated oil, inorganic compound, and oxidant.

[0007] The present invention discovers that a coordination interaction can be formed between the carboxyl groups in unsaturated oils and inorganic salt ions, and under the action of an oxidizing agent and water molecules, they can produce a high-strength underwater adhesion performance. Among them, unsaturated oils, as organic small molecules, have carboxyl groups, alkyl long chains, and unsaturated carbon-carbon double bonds, and can undergo a self-crosslinking reaction under the action of oxygen; inorganic cement materials are composed of inorganic compounds with hydration characteristics and can react with water, transforming from an amorphous state to a crystalline state. Unsaturated oils, as the hydrophobic part, expel interfacial water molecules, and inorganic compounds, as the hydrophilic part, absorb water for reaction. The dual action of the two effectively destroys the interfacial hydration layer and forms good interfacial contact. This colloid can have various action mechanisms with the substrate to be bonded, such as coordination, hydrogen bonding, hydrophobic, ionic, etc., endowing the adhesive with a wide range of multifunctional adhesion forces. At the same time, the synergistic effect of unsaturated oils and inorganic compounds forms an underwater adhesive with ultra-high strength, durability, stability, and wide applicability.

[0008] Further, the mass ratio of the unsaturated oil, inorganic compound, and oxidizing agent is 100:(1 - 150):(0.1 - 10).

[0009] More preferably, the mass ratio of the unsaturated oil, inorganic compound, and oxidizing agent is 100:(25 - 150):(0.1 - 10).

[0010] Further, the unsaturated oils include palmitoleic acid, oleic acid, linoleic acid, eleostearic acid, dimer acid, ricinoleic acid, etc.

[0011] Further, the oxidizing agents include hydrogen peroxide (concentration 3 - 30 wt%), potassium permanganate solution (concentration 0.01 - 0.5 wt%), and dichromate solution (concentration 0.1 - 0.5 mol / L).

[0012] The inorganic compounds include inorganic salts and inorganic oxides with hydration characteristics, specifically including raw materials for Portland cement (mainly containing tricalcium silicate, dicalcium silicate, etc.), raw materials for sulfoaluminate cement (mainly containing calcium sulfoaluminate, dicalcium silicate, etc.), and raw materials for magnesium salt cement (mainly containing magnesium chloride, magnesium oxide, etc.).

[0013] The present invention also provides a preparation method for the above-mentioned underwater adhesive based on biomimetic mineralized organic-inorganic hybridization, that is, under room temperature and solvent-free conditions, the unsaturated oil and inorganic compound are mixed and stirred until a yellow viscous colloid is formed, then the oxidizing agent is added and stirred until evenly mixed, and finally it is used in an underwater environment. Further, the mixing and stirring time of the unsaturated oil and inorganic compound is 5 - 10 minutes, and the stirring time after adding the oxidizing agent is 5 - 8 minutes.

[0014] The present invention also provides an application of the above-mentioned underwater adhesive based on biomimetic mineralization organic-inorganic hybridization.

[0015] Furthermore, the application includes bonding or repairing stainless steel, glass, plastics, rubber, etc. underwater.

[0016] The beneficial effects of the present invention are as follows:

[0017] 1. The present invention uses an oxidant to promote the oxidative self-crosslinking of unsaturated oils and fats, and utilizes water molecules to induce the hydration hardening of inorganic compounds. The above two points endow the adhesive with the function of rapid in-situ curing at room temperature.

[0018] 2. The adhesive system of the present invention has both excellent interfacial adhesion performance and cohesive performance in the body, realizing strong and stable bonding.

[0019] 3. The raw materials selected in the present invention are widely sourced, low in price, and environmentally friendly; the preparation of the adhesive adopts a one-step solvent-free method, which is simple to operate, does not require complex synthesis and toxic solvents, and is suitable for industrial scale production.

[0020] 4. The adhesive of the present invention has high bonding strength for various substrates, and has remarkable stability and environmental adaptability, and can be used for a long time in extreme environments such as acidic, alkaline, and seawater.

[0021] 5. The adhesive of the present invention is used for underwater repair, meets the requirements of underwater operations, and can be applied to the construction of underwater structures, the repair of damaged containers and water pipes, etc. Description of the Drawings

[0022] Figure 1 It is the bonding strength of the adhesive prepared in Example 1 of the present invention for different substrates and different aqueous solution environments, and for stainless steel, glass, polyvinyl chloride, polytetrafluoroethylene, polypropylene, acrylic, polyethylene, and rubber cured for 18 hours under the condition of no curing pressure.

[0023] Figure 2 It is a schematic design diagram of the oyster-mimicking mineralized adhesive proposed by the present invention. Detailed Embodiments

[0024] The following combines the embodiments of the present invention to detail the technical solutions in the embodiments of the present invention, but the protection scope is not limited thereto.

[0025] Example 1

[0026] This example provides an underwater adhesive based on biomimetic mineralization organic-inorganic hybridization. The adhesive is prepared according to the following weight ratio:

[0027]

[0028] The preparation method is as follows:

[0029] Dissolve 4.7 g of magnesium chloride and 10 g of magnesium oxide in 10 g of dimer acid. After stirring for 10 minutes at room temperature until evenly mixed, add 1 g of hydrogen peroxide solution with a concentration of 10 wt%, and continue to stir for 6 minutes at room temperature to finally form a yellow viscous colloid.

[0030] Example 2

[0031] This example provides an underwater adhesive based on biomimetic mineralization organic-inorganic hybridization. The adhesive is prepared according to the following weight ratio:

[0032]

[0033] The preparation method is as follows:

[0034] Dissolve 1.18 g of magnesium chloride and 2.5 g of magnesium oxide in 10 g of tung oil acid. After stirring for 10 minutes at room temperature until evenly mixed, add 1 g of hydrogen peroxide solution with a concentration of 10 wt%, and continue to stir for 6 minutes at room temperature to finally form a yellow viscous colloid.

[0035] Test Example 1

[0036] The lap shear strength was detected by the lap joint method. Apply the adhesive on the substrate underwater, with the glue application area being 25×25 mm 2 , the glue application amount being 0.15 g. Glue two substrates together underwater and place them in water for curing for 18 h without curing pressure. After curing, use a universal mechanical testing machine to test the lap shear strength at a tensile rate of 20 mm / s, that is, the bonding strength.

[0037] Table 1 shows the bonding strengths of the adhesives of Examples 1-2 of the present invention to stainless steel, glass, polyvinyl chloride, and polytetrafluoroethylene at room temperature.

[0038] Table 1

[0039]

[0040] The results show that the adhesives of the present invention exhibit excellent underwater bonding performance for stainless steel, glass, and polyvinyl chloride.

[0041] At room temperature, apply the adhesive prepared in Example 1 of the present invention to stainless steel, polyvinyl chloride, acrylic, glass, polytetrafluoroethylene, rubber, polyethylene, and polypropylene in water, seawater, acidic aqueous solution (pH = 3), and alkaline aqueous solution (pH = 10) at room temperature, and place them for 18 h without curing pressure. Test the bonding strength according to the method of this test example, and the results are shown in Figure 1The results show that the adhesive of the present invention exhibits excellent bonding strength for various substrates in different aqueous solution environments.

[0042] Test Example 2

[0043] Under room temperature conditions, the adhesive prepared in Example 1 of the present invention was applied to different substrates (stainless steel, polyvinyl chloride, acrylic, glass, polytetrafluoroethylene, rubber, polyethylene, polypropylene) in different solutions (seawater, water, acidic solution, alkaline solution), and cured for 18 h under no curing pressure. The bonding strength was tested according to the method of Test Example 1, and the results are shown in Table 2-5.

[0044] Table 2 shows the bonding strength of the adhesive prepared in Example 1 of the present invention for different substrates when placed in seawater for 18 hours, 30 days, and 3 months.

[0045] Table 2

[0046]

[0047] Table 3 shows the bonding strength of the adhesive prepared in Example 1 of the present invention for different substrates when placed underwater for 18 hours, 30 days, and 3 months.

[0048] Table 3

[0049]

[0050]

[0051] Table 4 shows the bonding strength of the adhesive prepared in Example 1 of the present invention for different substrates when placed in an acidic aqueous solution (pH = 3) for 18 hours, 30 days, and 3 months.

[0052] Table 4

[0053]

[0054] Table 5 shows the bonding strength of the adhesive prepared in Example 1 of the present invention for different substrates when placed in an alkaline aqueous solution (pH = 10) for 18 hours, 30 days, and 3 months.

[0055] Table 5

[0056]

[0057] The results show that the adhesive of the present invention was placed in different solutions for 3 months, and for most substrates, its bonding strength was comparable to that after curing for 18 h, showing excellent durability.

[0058] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. These modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An underwater adhesive based on biomimetic mineralization organic-inorganic hybridization, characterized in that: The components of the underwater adhesive include: unsaturated oil, inorganic compound and oxidant.

2. The underwater adhesive based on biomimetic mineralization organic-inorganic hybridization according to claim 1, characterized in that: The mass ratio of unsaturated oil, inorganic compound and oxidant is 100:(1-150):(0.1-10).

3. The underwater adhesive based on biomimetic mineralization organic-inorganic hybridization according to claim 1, characterized in that: The unsaturated oils include palmitoleic acid, oleic acid, linoleic acid, eleostearic acid, dimer acid and ricinoleic acid.

4. The underwater adhesive based on biomimetic mineralization organic-inorganic hybridization according to claim 1, characterized in that: The oxidant includes hydrogen peroxide, potassium permanganate solution and dichromate solution.

5. The underwater adhesive based on biomimetic mineralization organic-inorganic hybridization according to claim 1, characterized in that: The inorganic compounds include inorganic salts and inorganic oxides having hydration properties.

6. The underwater adhesive based on biomimetic mineralization organic-inorganic hybridization according to claim 5, characterized in that: The inorganic compounds include silicate cement raw materials, sulphoaluminate cement raw materials and magnesium salt cement raw materials.

7. The underwater adhesive based on biomimetic mineralization organic-inorganic hybridization according to claim 6, characterized in that: The main components of the silicate cement raw materials include tricalcium silicate and dicalcium silicate; the main components of the sulphoaluminate cement raw materials include calcium sulphoaluminate and dicalcium silicate; the main components of the magnesium salt cement raw materials include magnesium chloride and magnesium oxide.

8. The method for preparing the underwater adhesive based on biomimetic mineralization organic-inorganic hybridization according to any one of claims 1 to 7, characterized in that: Under solvent-free conditions at room temperature, unsaturated oils and inorganic compounds are mixed and stirred until a yellow viscous colloid is formed, and then an oxidant is added and stirred until the mixture is uniform, and finally it is used in an underwater environment.

9. The method for preparing the underwater adhesive based on biomimetic mineralization organic-inorganic hybridization according to claim 8, characterized in that: The mixing time of the unsaturated oil and the inorganic compound is 5-10 minutes, and the mixing time after adding the oxidant is 5-8 minutes.

10. The use of the underwater adhesive according to any one of claims 1 to 7, characterized in that: The applications include underwater bonding or repairing of stainless steel, glass, plastic, rubber.

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