CN117384573A - Underwater adhesive with selective adhesion and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of adhesives, in particular to an underwater adhesive with selective adhesion and a preparation method thereof. The underwater adhesive comprises the following raw materials in parts by weight: the underwater adhesive has the advantages of selective adhesion, good coating performance, high bonding strength, no need of special curing conditions such as ultraviolet light, high temperature and the like, direct use, no environmental pollution, convenient use and wide application prospect, and comprises 30-80 parts of acrylic ester monomers, 1-60 parts of monomers containing double bonds, 0.5-3 parts of dispersing agents, 0.5-3 parts of crosslinking agents and 0.5-3 parts of initiators.

Description

Underwater adhesive with selective adhesion and preparation method thereof

Technical Field

The invention relates to the technical field of adhesives, in particular to an underwater adhesive with selective adhesion and a preparation method thereof.

Background

The underwater adhesive with selective adhesion is one of hot spots for adhesive research, and the action mechanism of the adhesive is often to use intermolecular force to be easily damaged by water, so that the underwater adhesive with selective adhesion becomes a difficulty in adhesive research. Along with development and utilization of ocean resources by human beings, requirements on ocean engineering are continuously improved, particularly, requirements on underwater adhesives with selective adhesion are also continuously increased, however, the adhesives are soaked in water for a long time, continuous permeation of water molecules leads to plasticization, expansion, erosion, degradation or hydrolysis of the adhesives, finally, bonding failure is caused, and safety and reliability of ocean engineering are seriously threatened.

The research direction of the underwater adhesives with selective adhesion is mainly focused on the development and application of novel materials, such as two-component adhesives, photo-curing adhesives, thermosetting adhesives and the like. For example, patent number CN200910017155.5 discloses an underwater epoxy adhesive and a preparation method thereof, which can bond plastic flexible filler conforming to national standard GB/T23864-2009 in water, but does not relate to specific information such as bonding strength, curing speed and the like.

Patent No. 201310519650.2 discloses an adhesive special for underwater construction and a preparation method thereof, which are applied to the construction of hydraulic engineering and environmental management engineering and the repair of underground concrete facilities and pipelines of buildings, but the curing time is longer, and the specific information of whether the product has selective adsorption capacity or not and whether the product is suitable for underwater bonding of plastic products and the desorption performance of the plastic products is not involved.

Patent No. 202110876567.5 discloses an underwater adhesive with selective adhesion of palm oil base, which has shear strengths of 95kPa, 76kPa, 71kPa, 72kPa and 78kPa for metals, wood, polytetrafluoroethylene, glass and plastics under water, respectively, but has a shear strength which is difficult to be comparable with the bonding strength in the air, and a desorption method is not mentioned, and a preparation method thereof.

Therefore, the existing selective adhesion underwater adhesives have the advantages and disadvantages of long curing time, lower adhesion, poor environmental adaptability, poor durability, higher cost and the like. The polymer material, particularly the plastic product, has replaced materials such as metal in many fields, especially in the ocean environment, the polymer material replaces the metal material, can solve the electrochemical corrosion difficult problem of the metal material effectively.

Therefore, aiming at the needs of underwater repair, adhesion and the like of high polymer materials, development of an underwater adhesive with selective adhesion to metal materials, high adhesion speed, high adhesion strength and easy desorption under specific conditions is needed.

Disclosure of Invention

The invention aims to at least solve one of the technical problems in the prior art and provides an underwater adhesive with selective adhesion and a preparation method thereof.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: an underwater adhesive with selective adhesion comprises the following raw materials in parts by weight: comprises 30 to 80 parts of acrylic monomer, 1 to 60 parts of monomer containing double bonds, 0.5 to 3 parts of dispersing agent, 0.5 to 3 parts of cross-linking agent and 0.5 to 3 parts of initiator.

Further, the acrylic ester monomer comprises one or more of octadecyl methacrylate, hexadecyl methacrylate, tetradecyl methacrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate and butyl acrylate.

Further, the monomer containing double bond comprises one or more of styrene, ethylene, butadiene and octavinyl silsesquioxane.

Further, the dispersing agent comprises one or more of polyvinyl alcohol, polyethylene glycol, polyacrylic acid or sodium dodecyl benzene sulfonate.

Further, the cross-linking agent is pentaerythritol tetraacrylate or pentaerythritol tetra (3-mercaptopropionic acid).

Further, the initiator is azobisisobutyronitrile or benzoyl peroxide.

The preparation method of the underwater adhesive with selective adhesion comprises the following steps:

s1, adding a polyvinyl alcohol aqueous solution and a certain amount of deionized water into a four-neck flask with a condensing system, mechanically stirring at a rotating speed of 250-350 r/min for 10-40 min and heating to 40-60 ℃;

s2, ultrasonically oscillating the acrylic monomer, the cross-linking agent, the initiator and the organic solvent in a beaker for a period of time until the acrylic monomer and the cross-linking agent are completely dispersed to form uniform reaction liquid drops;

s3, dropwise adding the mixed solution in the step S2 into the polyvinyl alcohol aqueous solution in the step S1, and adding deionized water when the mixed solution in the system is milky white at the rotating speed of 350-600 r/min;

s4, introducing argon for 15min, heating to 60-90 ℃ and starting the reaction;

s5, stopping the reaction after the polymerization reaction is carried out for 5-10 hours, cooling the reaction to room temperature, and filtering the reaction product by using a stainless steel screen to obtain the adhesive;

s6, washing and soaking the adhesive prepared in the step S5 with deionized water and absolute ethyl alcohol in sequence, and removing unreacted monomers and surfactant;

s7, removing most of ethanol in the adhesive by suction filtration, and drying for 9-15 hours at the temperature of 40-65 ℃ to obtain the pure adhesive.

Further, the organic solvent comprises one or more of toluene, acetone and ethyl acetate.

As can be seen from the above description of the present invention, compared with the prior art, the present invention has the following advantages:

1. the invention has stable process, simple preparation method and low cost, and can realize industrial production.

2. The underwater adhesive with selective adhesion prepared by the invention has good coating performance and high bonding strength, does not need special curing conditions such as ultraviolet light, high temperature and the like, can be directly used, and does not pollute the environment.

3. The underwater adhesive with selective adhesion prepared by the invention has the characteristic of selective adhesion, only common high polymer materials are adhered, and the adhesive strength is high, such as polypropylene (PP), polyethylene (PE), polystyrene (PS) and the like, and after the polypropylene (PP), the Polyethylene (PE) and the Polystyrene (PS) are respectively adhered under water, the underwater adhesive is continuously soaked in an underwater environment at 25 ℃ for 24 hours, and the shearing strength is measured to be 759.8KPa, 986.5KPa and 685.3KPa respectively, which are obviously higher than that of the common underwater adhesive with selective adhesion, and in addition, the adhesive has no adhesive strength to materials such as wood, glass, ceramics, stainless steel and the like.

4. The underwater adhesive with selective adhesion prepared by the invention has excellent water resistance and durability: after high polymer materials such as polypropylene (PP), polyethylene (PE), polystyrene (PS) and the like are continuously glued in a marine environment for 20 days, no obvious change is found in the shear strength; the adhesive also has excellent adhesive property and durability under the acid-base environment with pH value of 2 and 10; stable adhesive properties are developed after long-term use in seawater environments at 5 ℃,15 ℃ and 25 ℃.

5. The underwater adhesive with selective adhesion prepared by the invention has the characteristic of easy stripping under specific conditions, for example, one or more of silicone oil, vegetable oil, mineral oil, lubricating oil and the like can be easily stripped within a few seconds only by dripping the silicone oil, vegetable oil, mineral oil, lubricating oil and the like at an adhesion interface.

6. The underwater adhesive with selective adhesion prepared by the invention has reusability, and the adsorbed oil can be removed after desorption, so that the adhesive can be used for adhesion again, and the shear strength is not obviously changed.

Drawings

FIG. 1 is a graph of shear strength under water of an underwater adhesive having selective adhesion in a preferred embodiment of the present invention.

Detailed Description

The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention.

Example 1

The preparation method of the underwater adhesive with selective adhesion comprises the following preparation steps:

s1, weighing 3mL of 5% polyvinyl alcohol aqueous solution and 30mL of deionized water, mechanically stirring in a four-neck flask with a condensing system, wherein the rotating speed is 300r/min, the time is 20min, and the temperature is raised to 50 ℃, so that the reaction can be promoted;

s2, weighing 45 parts of styrene, 60 parts of dodecyl acrylate, 45 parts of butyl acrylate, 45 parts of ethyl acetate, 1.5 parts of pentaerythritol tetraacrylate and 1.5 parts of octavinyl silsesquioxane in a beaker, completely dissolving 1.5 parts of azobisisobutyronitrile in an ethanol solution, adding the ethanol solution into the beaker, and carrying out ultrasonic oscillation for a period of time until the azobisisobutyronitrile is completely dispersed to form uniform reaction liquid drops, thereby ensuring the full progress of the reaction and avoiding side reactions;

s3, dropwise adding the mixed solution in the step S2 into the polyvinyl alcohol aqueous solution, stirring at the rotating speed of 450r/min until the mixed solution in the system is milky white, and adding 35mL of deionized water to promote the reaction to be fully carried out, so that the reaction is prevented from agglomerating to influence the subsequent polymerization reaction;

s4, introducing argon for 15min, heating to 80 ℃ and starting the reaction;

s5, stopping the reaction after 8 hours of polymerization, cooling the reaction to room temperature, and filtering the reaction product by using a stainless steel screen to obtain an adhesive;

s6, washing and soaking the prepared adhesive with deionized water and absolute ethyl alcohol in sequence, and removing unreacted monomers and surfactant;

s7, removing most of ethanol in the adhesive by suction filtration, and drying at 60 ℃ for 12 hours to obtain the pure adhesive.

Example 2

The preparation method of the underwater adhesive with selective adhesion comprises the following preparation steps:

s1, weighing 3mL of 5% polyvinyl alcohol aqueous solution and 30mL of deionized water, mechanically stirring in a four-neck flask with a condensing system, wherein the rotating speed is 300r/min, the time is 20min, and the temperature is raised to 50 ℃, so that the reaction can be promoted;

s2, weighing 45 parts of styrene, 60 parts of dodecyl acrylate, 45 parts of butyl acrylate, 45 parts of toluene, 1.5 parts of pentaerythritol tetraacrylate and 1.5 parts of octavinyl silsesquioxane in a beaker, completely dissolving 1.5 parts of azobisisobutyronitrile into an ethanol solution, adding the ethanol solution into the beaker, and carrying out ultrasonic oscillation for a period of time until the azobisisobutyronitrile is completely dispersed to form uniform reaction liquid drops, thereby ensuring the full progress of the reaction and avoiding side reactions;

s3, dropwise adding the mixed solution in the step S2 into the polyvinyl alcohol aqueous solution, stirring at the rotating speed of 450r/min until the mixed solution in the system is milky white, and adding 35mL of deionized water to promote the reaction to be fully carried out, so that the reaction is prevented from agglomerating to influence the subsequent polymerization reaction;

s4, introducing argon for 15min, heating to 80 ℃ and starting the reaction;

s5, stopping the reaction after 8 hours of polymerization, cooling the reaction to room temperature, and filtering the reaction product by using a stainless steel screen to obtain an adhesive;

s6, washing and soaking the prepared adhesive with deionized water and absolute ethyl alcohol in sequence, and removing unreacted monomers and surfactant;

s7, removing most of ethanol in the adhesive by suction filtration, and drying at 60 ℃ for 12 hours to obtain the pure adhesive.

Example 3

The preparation method of the underwater adhesive with selective adhesion comprises the following preparation steps:

s1, weighing 3mL of 5% polyvinyl alcohol aqueous solution and 30mL of deionized water, mechanically stirring in a four-neck flask with a condensing system, wherein the rotating speed is 300r/min, the time is 20min, and the temperature is raised to 50 ℃, so that the reaction can be promoted;

s2, weighing 10 parts of styrene, 60 parts of dodecyl acrylate, 45 parts of butyl acrylate, 45 parts of ethyl acetate, 1.5 parts of pentaerythritol tetraacrylate and 1.5 parts of octavinyl silsesquioxane in a beaker, completely dissolving 1.5 parts of azobisisobutyronitrile in an ethanol solution, adding the ethanol solution into the beaker, and carrying out ultrasonic oscillation for a period of time until the azobisisobutyronitrile is completely dispersed to form uniform reaction liquid drops, thereby ensuring the full progress of the reaction and avoiding side reactions;

s3, dropwise adding the mixed solution in the step S2 into the polyvinyl alcohol aqueous solution, stirring at the rotating speed of 450r/min until the mixed solution in the system is milky white, and adding 35mL of deionized water to promote the reaction to be fully carried out, so that the reaction is prevented from agglomerating to influence the subsequent polymerization reaction;

s4, introducing argon for 15min, heating to 80 ℃ and starting the reaction;

s5, stopping the reaction after 8 hours of polymerization, cooling the reaction to room temperature, and filtering the reaction product by using a stainless steel screen to obtain an adhesive;

s6, washing and soaking the prepared adhesive with deionized water and absolute ethyl alcohol in sequence, and removing unreacted monomers and surfactant;

s7, removing most of ethanol in the adhesive by suction filtration, and drying at 60 ℃ for 12 hours to obtain the pure adhesive.

Example 4

The preparation method of the underwater adhesive with selective adhesion comprises the following preparation steps:

s1, weighing 3mL of 5% polyvinyl alcohol aqueous solution and 30mL of deionized water, mechanically stirring in a four-neck flask with a condensing system, wherein the rotating speed is 300r/min, the time is 20min, and the temperature is raised to 50 ℃, so that the reaction can be promoted;

s2, weighing 45 parts of styrene, 60 parts of octadecyl methacrylate, 45 parts of butyl acrylate, 45 parts of toluene, 1.5 parts of pentaerythritol tetraacrylate and 1.5 parts of octavinyl silsesquioxane in a beaker, completely dissolving 1.5 parts of azobisisobutyronitrile in an ethanol solution, adding the ethanol solution into the beaker, and carrying out ultrasonic oscillation for a period of time until the azobisisobutyronitrile is completely dispersed to form uniform reaction liquid drops, thereby ensuring the full progress of the reaction and avoiding side reactions;

s3, dropwise adding the mixed solution in the step S2 into the polyvinyl alcohol aqueous solution, stirring at the rotating speed of 450r/min until the mixed solution in the system is milky white, and adding 35mL of deionized water to promote the reaction to be fully carried out, so that the reaction is prevented from agglomerating to influence the subsequent polymerization reaction;

s4, introducing argon for 15min, heating to 80 ℃ and starting the reaction;

s5, stopping the reaction after 8 hours of polymerization, cooling the reaction to room temperature, and filtering the reaction product by using a stainless steel screen to obtain an adhesive;

s6, washing and soaking the prepared adhesive with deionized water and absolute ethyl alcohol in sequence, and removing unreacted monomers and surfactant;

s7, removing most of ethanol in the adhesive by suction filtration, and drying at 60 ℃ for 12 hours to obtain the pure adhesive.

Example 5

The preparation method of the underwater adhesive with selective adhesion comprises the following preparation steps:

s1, weighing 3mL of 5% polyvinyl alcohol aqueous solution and 30mL of deionized water, mechanically stirring in a four-neck flask with a condensing system, wherein the rotating speed is 300r/min, the time is 20min, and the temperature is raised to 50 ℃, so that the reaction can be promoted;

s2, weighing 45 parts of styrene, 60 parts of octadecyl methacrylate, 45 parts of butyl acrylate, 45 parts of ethyl acetate, 1.5 parts of pentaerythritol tetraacrylate and 1.5 parts of octavinyl silsesquioxane in a beaker, completely dissolving 1.5 parts of azobisisobutyronitrile in an ethanol solution, adding the ethanol solution into the beaker, and carrying out ultrasonic oscillation for a period of time until the azobisisobutyronitrile is completely dispersed to form uniform reaction liquid drops, thereby ensuring the full progress of the reaction and avoiding side reactions;

s3, dropwise adding the mixed solution in the step S2 into the polyvinyl alcohol aqueous solution, stirring at the rotating speed of 450r/min until the mixed solution in the system is milky white, and adding 35mL of deionized water to promote the reaction to be fully carried out, so that the reaction is prevented from agglomerating to influence the subsequent polymerization reaction;

s4, introducing argon for 15min, heating to 80 ℃ and starting the reaction;

s5, stopping the reaction after 8 hours of polymerization, cooling the reaction to room temperature, and filtering the reaction product by using a stainless steel screen to obtain an adhesive;

s6, washing and soaking the prepared adhesive with deionized water and absolute ethyl alcohol in sequence, and removing unreacted monomers and surfactant;

s7, removing most of ethanol in the adhesive by suction filtration, and drying at 60 ℃ for 12 hours to obtain the pure adhesive.

Example 6

The preparation method of the underwater adhesive with selective adhesion comprises the following preparation steps:

s1, weighing 3mL of 5% polyvinyl alcohol aqueous solution and 30mL of deionized water, mechanically stirring in a four-neck flask with a condensing system, wherein the rotating speed is 300r/min, the time is 20min, and the temperature is raised to 50 ℃, so that the reaction can be promoted;

s2, weighing 45 parts of styrene, 60 parts of octadecyl methacrylate, 45 parts of butyl acrylate, 45 parts of ethyl acetate, 1.5 parts of pentaerythritol tetraacrylate and 1.5 parts of octavinyl silsesquioxane in a beaker, completely dissolving 1.5 parts of azobisisobutyronitrile in an ethanol solution, adding the ethanol solution into the beaker, and carrying out ultrasonic oscillation for a period of time until the azobisisobutyronitrile is completely dispersed to form uniform reaction liquid drops, thereby ensuring the full progress of the reaction and avoiding side reactions;

s3, dropwise adding the mixed solution in the step S2 into the polyvinyl alcohol aqueous solution, stirring at the rotating speed of 450r/min until the mixed solution in the system is milky white, and adding 35mL of deionized water to promote the reaction to be fully carried out, so that the reaction is prevented from agglomerating to influence the subsequent polymerization reaction;

s4, introducing argon for 15min, heating to 70 ℃ and starting the reaction;

s5, stopping the reaction after 8 hours of polymerization, cooling the reaction to room temperature, and filtering the reaction product by using a stainless steel screen to obtain an adhesive;

s6, washing and soaking the prepared adhesive with deionized water and absolute ethyl alcohol in sequence, and removing unreacted monomers and surfactant;

s7, removing most of ethanol in the adhesive by suction filtration, and drying at 60 ℃ for 12 hours to obtain the pure adhesive.

The adhesive strength test results of the above examples are shown in table 1, and after sandwiching the adhesive between two substrates in water and immersing for 24 hours in an underwater environment at 25 ℃, a tensile tester was used to perform shear strength test, and each component was adhered to different materials three times to average.

Table 1: shear Strength test of samples (Unit: KPa)

The adhesive strength test described above revealed that: the underwater adhesive with selective adhesion prepared by the invention has selective adhesion and high adhesion strength. After high polymer materials such as polypropylene (PP), polyethylene (PE), polystyrene (PS) and the like are continuously glued in a marine environment for 20 days, no obvious change is found in the shear strength; the adhesive also has excellent adhesive property and durability under the acid-base environment with pH value of 2 and 10; stable adhesive properties are developed after long-term use in seawater environments at 5 ℃,15 ℃ and 25 ℃.

The above additional technical features can be freely combined and superimposed by a person skilled in the art without conflict.

It will be understood that the invention has been described in terms of several embodiments, and that various changes and equivalents may be made to these features and embodiments by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (8)

1. The underwater adhesive with selective adhesion is characterized by comprising the following raw materials in parts by weight: comprises 30 to 80 parts of acrylic monomer, 1 to 60 parts of monomer containing double bonds, 0.5 to 3 parts of dispersing agent, 0.5 to 3 parts of cross-linking agent and 0.5 to 3 parts of initiator.

2. The selectively adhering underwater adhesive of claim 1 wherein: the acrylic ester monomer comprises one or more of octadecyl methacrylate, hexadecyl methacrylate, tetradecyl methacrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate and butyl acrylate.

3. The selectively adhering underwater adhesive of claim 1 wherein: the monomer containing double bonds comprises one or more of styrene, ethylene, butadiene and octavinyl silsesquioxane.

4. The selectively adhering underwater adhesive of claim 1 wherein: the dispersing agent comprises one or more of polyvinyl alcohol, polyethylene glycol, polyacrylic acid or sodium dodecyl benzene sulfonate.

5. The selectively adhering underwater adhesive of claim 1 wherein: the cross-linking agent is pentaerythritol tetraacrylate or pentaerythritol tetra (3-mercaptopropionic acid).

6. The selectively adhering underwater adhesive of claim 1 wherein: the initiator is azobisisobutyronitrile or benzoyl peroxide.

7. A preparation method of an underwater adhesive with selective adhesion is characterized by comprising the following steps: a method for preparing the selectively adhering underwater adhesive as claimed in any one of claims 1 to 6, comprising the steps of:

s1, adding a polyvinyl alcohol aqueous solution and a certain amount of deionized water into a four-neck flask with a condensing system, mechanically stirring at a rotating speed of 250-350 r/min for 10-40 min and heating to 40-60 ℃;

s2, ultrasonically oscillating the acrylic monomer, the cross-linking agent, the initiator and the organic solvent in a beaker for a period of time until the acrylic monomer and the cross-linking agent are completely dispersed to form uniform reaction liquid drops;

s3, dropwise adding the mixed solution in the step S2 into the polyvinyl alcohol aqueous solution in the step S1, and adding deionized water when the mixed solution in the system is milky white at the rotating speed of 350-600 r/min;

s4, introducing argon for 15min, heating to 60-90 ℃ and starting the reaction;

s5, stopping the reaction after the polymerization reaction is carried out for 5-10 hours, cooling the reaction to room temperature, and filtering the reaction product by using a stainless steel screen to obtain the adhesive;

s6, washing and soaking the adhesive prepared in the step S5 with deionized water and absolute ethyl alcohol in sequence, and removing unreacted monomers and surfactant;

s7, removing most of ethanol in the adhesive by suction filtration, and drying for 9-15 hours at the temperature of 40-65 ℃ to obtain the pure adhesive.

8. The method for preparing the underwater adhesive with selective adhesion according to claim 7, wherein: the organic solvent comprises one or more of toluene, acetone and ethyl acetate.