Antifouling gel particles and preparation method thereof

Abstract

The present invention provides an antifouling gel particle and a preparation method thereof, wherein the antifouling gel particle comprises the following components by weight: 10 to 20 parts of acrylamide monomers; 10 to 20 parts of acrylic acid-based monomers; 3 to 5 parts of graphene functional materials; 0.1 to 0.5 parts of crosslinking agents; 0.2 to 0.7 parts of initiators; 0.1 to 0.5 parts of catalysts; 50 to 70 parts of deionized water; the graphene functional materials include graphene oxide, rare earth cerium solution and isothiazolinone antifouling agents; and an acrylic acid double bond structure is grafted on the surface of graphene oxide. In the antifouling gel particles of the present invention, graphene oxide, rare earth cerium solution, isothiazolinone antifouling agents and hydrogels have synergistic effects to achieve a triple antifouling mechanism, thereby improving the antifouling and antibacterial efficiency; graphene oxide has a slow-release characteristic, which can effectively control the seepage of the antifouling agent and achieve a lasting antifouling effect; and the mechanical properties of the antifouling gel particles are improved.

Description

Technical Field

[0001] The invention relates to the field of chemical materials, and in particular to antifouling gel particles and a preparation method thereof. Background Art

[0002] During the application process in the marine environment, biological fouling is easy to form on the surface of ships, bridges, oil drilling platforms, pipelines and other equipment and facilities, which will not only increase the navigation resistance of ships, increase fuel consumption, accelerate material corrosion, etc., but also increase greenhouse gas emissions and affect climate change. At present, coating their surfaces with antifouling coatings is still the most economical and effective way to solve the fouling problem.

[0003] Traditional antifouling coatings are mainly self-polishing antifouling coatings with high content of antifouling agents, which rely on the seepage of antifouling agents to poison and inhibit the growth of marine biofouling. However, studies have shown that the long-term release of high-concentration antifouling agents is prone to accumulate in large quantities in seaports, seriously damaging the marine environment. Therefore, the development of an antifouling gel particle and its preparation method, a new type of low-toxic and efficient environmentally friendly long-lasting antifouling coating is an urgent need for the development of a new generation of marine strategic development.

[0004] With the continuous development of new materials, hydrophilic gel materials can form a very thin hydration layer on the surface when used in the marine environment due to their super water absorption, which effectively prevents protein fouling organisms from adsorbing on their surface. It is one of the current research hotspots of environmentally friendly antifouling coatings. Rare earth elements have a special electronic layer structure, which can easily catalyze the production of free radicals with strong activity. At the same time, they have the unique characteristic of strong penetration into the body, which can effectively penetrate the cell membrane and promote the rapid entry of antibacterial substances into the cell. When compounded with antifouling agents, they can greatly improve the antifouling efficiency and have broad development prospects. In addition, graphene is a new type of sheet nanomaterial for antifouling gel particles and their preparation methods. Its high specific surface area provides a natural carrier material for antifouling agent loading, which can effectively control the release of antifouling agents and prolong the antifouling effect. At the same time, as early as 2010, researchers proposed that the sharp edges of graphene nanomaterials would lead to the destruction of cell membranes and the loss of RNA in cells. Therefore, graphene, as an antifouling material, is receiving increasing attention from experts in related fields.

[0005] The patent with application number CN202010857057.9 in the prior art discloses an antifouling gel particle containing rare earth / antifouling agent. First, the solvent-gel method is used to prepare white carbon black as a carrier. After modification by a silane coupling agent, a rare earth cerium solution is added to obtain a rare earth antibacterial white carbon black with good dispersibility. Then, the rare earth antibacterial white carbon black and the antifouling agent are co-coated by a free radical copolymerization method. The prepared antifouling gel has both hydrophilic antibacterial adhesion and antifouling agent bactericidal dual antifouling mechanism. However, the antifouling effect of the antifouling gel particles is limited, and the controlled release effect cannot be achieved, and the long-lasting antifouling cannot be achieved, and the mechanical properties of the antifouling material are poor.

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] The purpose of the present invention is to provide an antifouling gel particle and a preparation method thereof, so as to solve the problems in the prior art that the antifouling material has limited antifouling effect, cannot achieve controlled release effect, cannot achieve long-term antifouling and has poor mechanical properties.

[0008] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0009] An antifouling gel particle, comprising the following components in parts by weight:

[0010] 10-20 parts of acrylamide monomer;

[0011] 10-20 parts of acrylic acid-based monomer;

[0012] 3-5 parts of graphene functional material;

[0013] Cross-linking agent 0.1-0.5 parts;

[0014] Initiator 0.2-0.7 parts;

[0015] Catalyst 0.1-0.5 parts;

[0016] 50-70 parts of deionized water;

[0017] The graphene functional material comprises graphene oxide, rare earth cerium solution and isothiazolinone antifouling agent; and an acrylic acid double bond structure is grafted onto the surface of the graphene oxide.

[0018] The antifouling gel particles of the present invention first use graphene oxide as a carrier, graft an acrylic acid double bond structure on the surface of the graphene oxide so that the graphene oxide is activated, add a rare earth cerium solution and an isothiazolinone antifouling agent to prepare a graphene functional material, and then acrylamide monomers and acrylic acid monomers undergo free radical copolymerization under the action of a crosslinking agent, an initiator and a catalyst to obtain hydrogel-wrapped antifouling gel particles of graphite functional material. The graphene oxide, the rare earth cerium solution, the isothiazolinone antifouling agent and the hydrogel act synergistically to achieve a triple antifouling mechanism, which greatly improves the antifouling and antibacterial efficiency. The graphene oxide has a sustained release characteristic, and the release of the rare earth cerium solution and the isothiazolinone antifouling agent can be better controlled by the sheet structure of the graphene oxide, so that the antifouling agent seepage can be effectively controlled, the utilization efficiency of the antifouling agent can be improved, the antifouling life of the antifouling gel particles can be extended, and a lasting antifouling effect can be achieved. The acrylic acid double bond structure accessed on the surface of the graphene oxide is polymerized with the double bonds in the gel resin to form a chemical network structure, which significantly improves the mechanical properties of the antifouling gel particles.

[0019] Furthermore, the isothiazolinone antifouling agent is at least one of 2-methyl-4-isothiazoline-3-one, 4,5-dichloro-N-octyl-4-isothiazoline-3-one, and 1,2-benzisothiazolin-3-one.

[0020] Furthermore, the rare earth cerium solution is at least one of cerium nitrate and cerium sulfate.

[0021] Furthermore, the acrylamide monomer is at least one of acrylamide, N-isopropylacrylamide and N-diethylacrylamide.

[0022] Furthermore, the acrylic monomer is at least one of acrylic acid, hydroxypropyl methacrylate, and hydroxyethyl methacrylate.

[0023] Furthermore, the cross-linking agent is at least one of ethylene glycol dimethacrylate, N,N-methylenebisacrylamide, and oligoethylene glycol dimethacrylate.

[0024] Furthermore, the initiator is at least one of potassium persulfate, ammonium persulfate, azobisisobutylamidine hydrochloride, and VA044 initiator; and the catalyst is at least one of tetramethylethylenediamine and tetramethylhexanediamine.

[0025] In a second aspect of the present invention, a method for preparing antifouling gel particles is provided. The method for preparing antifouling gel particles is used to prepare any one of the antifouling gel particles described above. The method for preparing antifouling gel particles comprises the following steps:

[0026] S1. Preparation of graphene functional materials;

[0027] S2. Preparation of antifouling gel particles.

[0028] The method for preparing the antifouling gel particles of the present invention has simple process, abundant raw material sources and can effectively reduce production costs.

[0029] Further, step S1 includes the following steps:

[0030] S11, dissolving the isothiazolinone antifouling agent: adding the isothiazolinone antifouling agent into dimethyl sulfoxide solvent, stirring and dispersing into a 25%wt solution;

[0031] This operation facilitates the loading of isothiazolinone antifouling agents in graphene oxide.

[0032] S12, graphene loaded with rare earth cerium / isothiazolinone antifouling agent: freeze-dry graphene oxide and evenly disperse it in anhydrous DMF, and ultrasonically disperse it for 0.5h; then add acrylic isocyanate, and stir and react for 6h under nitrogen protection; then add rare earth cerium solution and isothiazolinone antifouling agent solution in sequence, and then ultrasonically disperse it for 2-5h, so that rare earth ions and antifouling agent are adsorbed between graphene layers;

[0033] In this operation, the graphene oxide is first freeze-dried and then evenly dispersed in anhydrous DMF. Ultrasonic dispersion for 0.5 h can effectively increase the interlayer distance between the graphene oxide sheets, providing sufficient space for the loading of rare earth cerium solution and isothiazolinone antifouling agent solution. Then, acrylic isocyanate is added and the reaction is stirred for 6 h under nitrogen protection, which can allow the graphene oxide surface to be connected to the acrylic double bond structure, facilitating the subsequent chemical crosslinking with the gel and improving the mechanical properties of the gel particles. Then, rare earth cerium solution and isothiazolinone antifouling agent solution are added in turn, followed by ultrasonic dispersion for 2 to 5 h, so that the rare earth ions and antifouling agents are adsorbed on the surface. The graphene interlayer makes it easy for the rare earth cerium solution and the isothiazolinone antifouling agent solution to be fully and evenly contacted and compounded after being loaded on the graphene oxide, forming a synergistic antifouling effect and improving the antifouling efficiency; on the other hand, after being loaded on the graphene oxide, the release of the rare earth cerium solution and the isothiazolinone antifouling agent can be better controlled through the graphene oxide sheet structure, thereby improving the utilization rate of the rare earth cerium solution and the isothiazolinone antifouling agent, thereby prolonging the antifouling effect; in addition, the graphene oxide has a hard texture and can further protect the rare earth cerium solution and the isothiazolinone antifouling agent solution.

[0034] S13, washing and drying: After the reaction is completed, the precipitate is obtained by centrifugation, and washed with deionized water for 2 to 3 times, and then the precipitate is vacuum dried at 120° C. for 2 h, crushed and ground into powder to obtain graphene functional material.

[0035] Further, step S2 includes the following steps:

[0036] S21, synthesis of free radical copolymer hydrophilic gel: add acrylamide monomer, acrylic acid monomer, graphene functional material, crosslinking agent, initiator and deionized water into a reaction kettle, stir and heat to 60-80°C, add 0.1-0.5 parts of catalyst into the reaction kettle after 10 minutes, continue stirring for 2-3 hours and then stop stirring, let stand at 10-20°C and continue to react for 1 hour to obtain gel;

[0037] S22, washing and drying: taking out the gel prepared in step S21, squeezing it into small pieces, washing it with deionized water for 2 to 3 times, drying it in an oven, and then grinding it in a high-energy ball mill for 10 hours to obtain the desired antifouling gel particles.

[0038] The present invention provides an antifouling gel particle and a preparation method thereof. Compared with the prior art, the antifouling gel particle and the preparation method thereof provided by the present invention have the following beneficial effects:

[0039] 1) The antifouling gel particles and the preparation method thereof described in the present invention are as follows: firstly, graphene oxide is used as a carrier, acrylic acid double bond structure is grafted on the surface of graphene oxide to activate graphene oxide, rare earth cerium solution and isothiazolinone antifouling agent are added to prepare graphene functional material, and then acrylamide monomer and acrylic acid monomer are subjected to free radical copolymerization reaction under the action of crosslinking agent, initiator and catalyst to obtain hydrogel-wrapped graphite functional material antifouling gel particles, graphene oxide, rare earth cerium solution, isothiazolinone antifouling agent and hydrogel The gel acts synergistically to achieve a triple antifouling mechanism, greatly improving the antifouling and antibacterial efficiency; the surface of the activated graphene oxide is connected to the acrylic double bond structure, which is polymerized with the double bonds in the gel resin to form a chemical network structure, thereby improving the mechanical properties of the antifouling gel particles; graphene oxide has a sustained release property, and the release of rare earth cerium solution and isothiazolinone antifouling agents can be better controlled through the lamellar structure of graphene oxide, which can effectively control the seepage of antifouling agents, improve the utilization efficiency of antifouling agents, extend the antifouling life of antifouling gel particles, and achieve a lasting antifouling effect.

[0040] 2) The antifouling gel particles and the preparation method thereof described in the present invention, graphene oxide, rare earth cerium solution, isothiazolinone antifouling agent and hydrogel have synergistic effect to realize triple antifouling mechanism, which greatly improves the antifouling and antibacterial efficiency. The hydrogel material, due to its super water absorption, can form a very thin hydration layer on the surface, effectively preventing the adsorption of fouling organisms on its surface, forming the first antifouling mechanism; once it is attached, it can be released by rare earth cerium and isothiazolinone antifouling agent, and rare earth cerium and isothiazolinone antifouling agent synergistically prevent fouling and quickly play a bactericidal role, forming the second antifouling mechanism; graphene oxide is a two-dimensional nanomaterial, and its sharp edge characteristics can produce a "nano knife" effect, which is conducive to destroying the phospholipids of the cell wall of fungi, etc., and has certain antibacterial properties, forming the third antifouling mechanism, which greatly improves the antifouling and antibacterial efficiency.

[0041] 3) The antifouling gel particles and the preparation method thereof described in the present invention, the graphene oxide functional material is modified by acrylic isocyanate, and is easily and evenly dispersed in the hydrogel system, and can become a chemically cross-linked skeleton, thereby improving the mechanical properties of the gel particles, that is, significantly enhancing the rigidity of the antifouling gel particles.

[0042] 4) The antifouling gel particles and the preparation method thereof described in the present invention have the unique characteristic that rare earth ions have strong penetration into the body, can effectively penetrate the cell membrane, promote the antibacterial substances to quickly reach the inside of the cell, denature the cell protein and complete the sterilization. The present invention uses rare earth cerium, and other rare earth materials can also be used for preparation, but on the one hand, rare earth cerium is the most abundant rare earth material in the earth's crust, and the raw materials are relatively easy to obtain.

[0043] 5) The antifouling gel particles and the preparation method thereof described in the present invention, the isothiazolinone antifouling agent can be rapidly degraded in the environment, has little impact on marine organisms, has little accumulation in the organism, is low in toxicity, has good antifouling effect and long service life.

[0044] 6) The antifouling gel particles and the preparation method thereof described in the present invention have simple process and abundant raw material sources, which can effectively reduce production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is a SEM photo of the graphene functional material in the antifouling gel particles described in an embodiment of the present invention. DETAILED DESCRIPTION

[0046] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The descriptions of "first", "second", etc. mentioned in the embodiments of the present invention are only for descriptive purposes, and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the ability of ordinary technicians in the field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0047] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0048] The technical problems to be solved by the present application are: (1) the problem of limited antifouling effect of antifouling materials, (2) the problem that antifouling materials cannot achieve controlled release effect and cannot achieve long-lasting antifouling effect; (3) the problem of poor mechanical properties of antifouling materials; and (4) the problem of poor stability and uniformity of the antifouling performance of antifouling gel particles at various locations.

[0049] An antifouling gel particle, comprising the following components by weight: 10-20 parts of acrylamide monomers; 10-20 parts of acrylic acid monomers; 3-5 parts of graphene functional materials; 0.1-0.5 parts of crosslinking agents; 0.2-0.7 parts of initiators; 0.1-0.5 parts of catalysts; 50-70 parts of deionized water; the graphene functional materials include graphene oxide, rare earth cerium solution and isothiazolinone antifouling agents. An acrylic acid double bond structure is grafted onto the surface of the graphene oxide.

[0050] The antifouling gel particles of the present invention first use graphene oxide as a carrier, graft an acrylic acid double bond structure on the surface of the graphene oxide so that the graphene oxide is activated, and then the acrylic acid double bond structure is grafted by reacting acrylic acid isocyanate with the hydroxyl group on the surface of the graphene oxide, and rare earth cerium solution and isothiazolinone antifouling agent are added to prepare graphene functional materials, and then acrylamide monomers and acrylic acid monomers undergo free radical copolymerization under the action of a crosslinking agent, an initiator and a catalyst to obtain hydrogel-wrapped antifouling gel particles of graphite functional materials, and the graphene oxide, rare earth cerium solution, isothiazolinone antifouling agent and hydrogel have a synergistic effect to achieve the antifouling effect. A triple antifouling mechanism is present, which greatly improves the antifouling and antibacterial efficiency; the surface of graphene oxide is connected with an acrylic double bond structure, which is polymerized with the double bonds in the gel resin to form a chemical network structure, which, on the one hand, improves the mechanical properties of the antifouling gel particles and the rigidity of the antifouling gel particles; on the other hand, it improves the stability and uniformity of the antifouling performance of the antifouling gel particles; graphene oxide has a sustained release characteristic, and the release of rare earth cerium solution and isothiazolinone antifouling agents can be better controlled through the lamellar structure of graphene oxide, which can effectively control the seepage of antifouling agents, improve the utilization efficiency of antifouling agents, extend the antifouling life of antifouling gel particles, and achieve a lasting antifouling effect.

[0051] In the present invention, graphene oxide plays the following roles:

[0052] (1) Graphene oxide has a high specific surface area and good drug loading characteristics, which greatly increases the loading amount of antifouling substances and improves the antifouling performance of antifouling gel particles.

[0053] (2) Graphene oxide has a sustained release property, which can effectively control the seepage of antifouling agents, improve the utilization efficiency of antifouling agents, extend the antifouling life of antifouling gel particles, and achieve a long-lasting antifouling effect.

[0054] (3) Graphene oxide is a two-dimensional nanomaterial with sharp edge characteristics, which can produce a "nano-knife" effect, which is beneficial for destroying the phospholipids in the cell walls of fungi and has certain antibacterial properties, thereby improving the antibacterial properties of antifouling gel particles.

[0055] (4) Graphene oxide is easily soluble in water, has good hydrophilicity, and has excellent dispersibility in water, which makes graphene oxide compatible with hydrogel and improves the hydrophilicity of antifouling gel particles;

[0056] (5) Graphene oxide functional materials can be uniformly dispersed in the hydrogel system without undergoing complex chemical modification, solving the dispersion problem of graphene oxide in the coating.

[0057] (6) Graphene oxide has abundant functional groups, such as hydroxyl, carboxyl, epoxy, amino, and carbonyl groups, which can form intramolecular and / or intermolecular hydrogen bonds with amide groups to form a stable network, thereby enhancing the mechanical properties of the antifouling gel particles, that is, enhancing the rigidity of the antifouling gel particles.

[0058] (7) Acrylic isocyanate reacts with the hydroxyl groups on the surface of graphene oxide to connect to the double bond structure of acrylic acid. The double bond structure is used as a chemical crosslinking point during the synthesis of the gel resin to form a stable chemical crosslinking network with the gel resin. On the one hand, the chemical crosslinking effect makes the position of graphene oxide in the hydrogel relatively fixed, thereby improving the stability and uniformity of the antifouling performance of the antifouling gel particles at various locations; on the other hand, the mechanical properties of the antifouling gel particles are improved.

[0059] Specifically, the isothiazolinone antifouling agent is at least one of 2-methyl-4-isothiazoline-3-one, 4,5-dichloro-N-octyl-4-isothiazoline-3-one, and 1,2-benzisothiazolin-3-one.

[0060] Specifically, the rare earth cerium solution is at least one of cerium nitrate and cerium sulfate.

[0061] Specifically, the acrylic isocyanate is at least one of ethyl isocyanate acrylate and ethyl isocyanate methacrylate.

[0062] Specifically, the acrylamide monomer is at least one of acrylamide, N-isopropylacrylamide and N-diethylacrylamide.

[0063] Specifically, the acrylic monomer is at least one of acrylic acid, hydroxypropyl methacrylate, and hydroxyethyl methacrylate.

[0064] Specifically, the cross-linking agent is at least one of ethylene glycol dimethacrylate, N,N-methylenebisacrylamide, and oligoethylene glycol dimethacrylate.

[0065] Specifically, the initiator is at least one of potassium persulfate, ammonium persulfate, azobisisobutylamidine hydrochloride, and VA044 initiator; the catalyst is at least one of tetramethylethylenediamine and tetramethylhexanediamine.

[0066] The present invention also provides a method for preparing antifouling gel particles. The method for preparing antifouling gel particles is used to prepare the antifouling gel particles described above. The method for preparing antifouling gel particles comprises the following steps:

[0067] S1. Preparation of graphene functional materials;

[0068] S2. Preparation of antifouling gel particles.

[0069] Specifically, step S1 includes the following steps:

[0070] S11, dissolving the isothiazolinone antifouling agent: adding the isothiazolinone antifouling agent into dimethyl sulfoxide solvent, stirring and dispersing into a 25%wt solution;

[0071] This operation facilitates the loading of isothiazolinone antifouling agents in graphene oxide.

[0072] S12, graphene loaded with rare earth cerium / isothiazolinone antifouling agent: freeze-dry graphene oxide and evenly disperse it in anhydrous DMF, and ultrasonically disperse it for 0.5h; then add ethyl isocyanate acrylate and stir the reaction under nitrogen protection for 6h; then ultrasonically disperse it for 2-5h to allow the rare earth ions and isothiazolinone antifouling agent to be adsorbed between the graphene layers;

[0073] In this operation, the graphene oxide is first freeze-dried and then evenly dispersed in anhydrous DMF. Ultrasonic dispersion for 0.5 h can effectively increase the interlayer distance between the graphene oxide sheets, providing sufficient space for the loading of rare earth cerium solution and isothiazolinone antifouling agent solution; then acrylic isocyanate is added, and the reaction is stirred for 6 h under nitrogen protection, so that the surface of the graphene oxide can be connected to the acrylic double bond structure, which is convenient for later chemical cross-linking with the gel. On the one hand, the effect of chemical cross-linking makes the position of the graphene oxide in the hydrogel relatively fixed, thereby improving the stability and uniformity of the antifouling performance of the antifouling gel particles; on the other hand, the rigidity of the antifouling gel particles is improved; then the rare earth cerium solution, isothiazolinone and the like are added in sequence. Ketone antifouling agent solution, and then ultrasonically disperse it for 2 to 5 hours to allow rare earth ions and antifouling agents to be adsorbed between graphene layers, so that after the rare earth cerium solution and the isothiazolinone antifouling agent solution are loaded on graphene oxide, it is convenient for the rare earth cerium solution and the isothiazolinone antifouling agent solution to fully and evenly contact and compound to form a synergistic antifouling effect, thereby improving the antifouling efficiency; on the other hand, after being loaded on graphene oxide, the release of rare earth cerium solution and isothiazolinone antifouling agent can be better controlled through the graphene oxide sheet structure, thereby improving the utilization rate of rare earth cerium solution and isothiazolinone antifouling agent, thereby prolonging the antifouling effect; in addition, graphene oxide has a hard texture and can further protect the rare earth cerium solution and isothiazolinone antifouling agent solution.

[0074] If the isothiazolinone antifouling agent is not loaded in graphene oxide, but is added during the synthesis of free radical copolymer hydrophilic gel, the isothiazolinone antifouling agent will be directly in the hydrogel, which may easily cause excessive release during the immersion in water, and the utilization rate of the isothiazolinone antifouling agent will be greatly reduced. On the other hand, the isothiazolinone antifouling agent will not be fully and evenly contacted with the rare earth cerium solution to form a synergistic antifouling effect, and the antifouling efficiency will also be greatly reduced.

[0075] Although graphene oxide is evenly dispersed in the hydrogel, the position of graphene oxide in the hydrogel is constantly changing, which drives the positions of rare earth cerium solution and isothiazolinone antifouling agents in the hydrogel to change continuously, resulting in the antifouling performance of various parts of the antifouling gel particles constantly changing, and the antifouling performance of various parts of the antifouling gel particles is unstable.

[0076] In order to solve the above problems, the graphene oxide used in the graphene functional material of the present invention is modified by grafting acrylic acid. The modified graphene oxide has an acrylic acid double bond structure, which can be used as a chemical crosslinking point to become the skeleton of the hydrogel. On the one hand, the chemical crosslinking makes the position of the graphene oxide in the hydrogel relatively fixed, thereby improving the stability and uniformity of the antifouling performance of the antifouling gel particles at various locations; on the other hand, the chemical crosslinking greatly enhances the strength of the antifouling gel particles.

[0077] S13, washing and drying: After the reaction is completed, the precipitate is obtained by centrifugation, and washed with deionized water 2 to 3 times, and then the precipitate is vacuum dried at 120° C. for 2 h, crushed and ground into powder, and a graphene functional material is obtained, such as Figure 1 shown.

[0078] Specifically, step S2 includes the following steps:

[0079] S21, synthesis of free radical copolymer hydrophilic gel: add acrylamide monomer, acrylic acid monomer, graphene functional material, crosslinking agent, initiator and deionized water into a reaction kettle, stir and heat to 60-80°C, add 0.1-0.5 parts of catalyst into the reaction kettle after 10 minutes, continue stirring for 2-3 hours and then stop stirring, let stand at 10-20°C and continue to react for 1 hour to obtain gel;

[0080] S22, washing and drying: taking out the gel prepared in step S21, squeezing it into small pieces, washing it with deionized water for 2 to 3 times, drying it in an oven, and then grinding it in a high-energy ball mill for 10 hours to obtain the desired antifouling gel particles.

[0081] The present invention is further described below with reference to specific examples, in which the addition amounts of various substances in the examples are all in parts by mass.

[0082] Table 1 Formula of raw materials for antifouling gel particles in the embodiment

[0083]

[0084]

[0085] Example 1

[0086] The preparation method of the antifouling gel particles in this embodiment is as follows: The types and addition amounts of the raw materials in the preparation method are shown in Table 1:

[0087] S1. Preparation of graphene functional materials;

[0088] S2. Preparation of antifouling gel particles.

[0089] Step S1 includes the following steps:

[0090] S11, dissolving the isothiazolinone antifouling agent: adding the isothiazolinone antifouling agent into dimethyl sulfoxide solvent, stirring and dispersing into a 25%wt solution;

[0091] S12, graphene loaded with rare earth cerium / isothiazolinone antifouling agent: freeze-dry graphene oxide and evenly disperse it in anhydrous DMF, and ultrasonically disperse it for 0.5h; then add ethyl isocyanate acrylate and stir the reaction under nitrogen protection for 6h; then ultrasonically disperse it for 2h to allow rare earth ions and isothiazolinone antifouling agent to be adsorbed between graphene layers;

[0092] S13, washing and drying: After the reaction is completed, the precipitate is obtained by centrifugation, and washed twice with deionized water. The precipitate is then vacuum dried at 120° C. for 2 h, crushed and ground into powder to obtain graphene functional material.

[0093] Step S2 includes the following steps:

[0094] S21, synthesis of free radical copolymer hydrophilic gel: add acrylamide monomer, acrylic acid monomer, graphene functional material, crosslinking agent, initiator and deionized water into a reactor, stir and heat to 60°C, add 0.1 parts of catalyst into the reactor after 10 minutes, continue stirring for 2 hours and then stop stirring, let stand at 10°C and continue to react for 1 hour to obtain gel;

[0095] S22, washing and drying: taking out the gel prepared in step S21, squeezing it into small pieces, washing it twice with deionized water, drying it in an oven, and then grinding it in a high-energy ball mill for 10 hours to obtain the desired antifouling gel particles.

[0096] Example 2

[0097] The preparation method of the antifouling gel particles in this embodiment is as follows: The types and addition amounts of the raw materials in the preparation method are shown in Table 1:

[0098] S1. Preparation of graphene functional materials;

[0099] S2. Preparation of antifouling gel particles.

[0100] Step S1 includes the following steps:

[0101] S11, dissolving the isothiazolinone antifouling agent: adding the isothiazolinone antifouling agent into dimethyl sulfoxide solvent, stirring and dispersing into a 25%wt solution;

[0102] S12, graphene loaded with rare earth cerium / isothiazolinone antifouling agent: freeze-dry graphene oxide and evenly disperse it in anhydrous DMF, and ultrasonically disperse it for 0.5h; then add ethyl isocyanate acrylate, and stir and react for 6h under nitrogen protection; then add rare earth cerium solution and isothiazolinone antifouling agent solution in sequence, and then ultrasonically disperse it for 3h, so that rare earth ions and isothiazolinone antifouling agent are adsorbed between graphene layers;

[0103] S13, washing and drying: After the reaction is completed, the precipitate is obtained by centrifugation, and washed twice with deionized water. The precipitate is then vacuum dried at 120° C. for 2 h, crushed and ground into powder to obtain graphene functional material.

[0104] Step S2 includes the following steps:

[0105] S21, synthesis of free radical copolymer hydrophilic gel: add acrylamide monomer, acrylic acid monomer, graphene functional material, crosslinking agent, initiator and deionized water into a reactor, stir and heat to 70°C, add 0.3 parts of catalyst into the reactor after 10 minutes, continue stirring for 2 hours and then stop stirring, let stand at 15°C and continue to react for 1 hour to obtain gel;

[0106] S22, washing and drying: taking out the gel prepared in step S21, squeezing it into small pieces, washing it twice with deionized water, drying it in an oven, and then grinding it in a high-energy ball mill for 10 hours to obtain the desired antifouling gel particles.

[0107] Example 3

[0108] The preparation method of the antifouling gel particles in this embodiment is as follows: The types and addition amounts of the raw materials in the preparation method are shown in Table 1:

[0109] S1. Preparation of graphene functional materials;

[0110] S2. Preparation of antifouling gel particles.

[0111] Step S1 includes the following steps:

[0112] S11, dissolving the isothiazolinone antifouling agent: adding the isothiazolinone antifouling agent into dimethyl sulfoxide solvent, stirring and dispersing into a 25%wt solution;

[0113] S12, graphene loaded with rare earth cerium / isothiazolinone antifouling agent: freeze-dry graphene oxide and evenly disperse it in anhydrous DMF, and ultrasonically disperse it for 0.5h; then add ethyl isocyanate acrylate, and stir and react for 6h under nitrogen protection; then add rare earth cerium solution and isothiazolinone antifouling agent solution in sequence, and then ultrasonically disperse it for 4h, so that rare earth ions and isothiazolinone antifouling agents are adsorbed between graphene layers;

[0114] S13, washing and drying: After the reaction is completed, the precipitate is obtained by centrifugation, and washed with deionized water for 3 times. The precipitate is then vacuum dried at 120° C. for 2 h, crushed and ground into powder to obtain graphene functional material.

[0115] Step S2 includes the following steps:

[0116] S21, synthesis of free radical copolymer hydrophilic gel: add acrylamide monomer, acrylic acid monomer, graphene functional material, crosslinking agent, initiator and deionized water into a reactor, stir and heat to 75°C, add 0.5 parts of catalyst into the reactor after 10 minutes, continue stirring for 2.8 hours and then stop stirring, let stand at 18°C ​​and continue to react for 1 hour to obtain gel;

[0117] S22, washing and drying: taking out the gel prepared in step S21, squeezing it into small pieces, washing it with deionized water for 3 times, drying it in an oven, and then grinding it in a high-energy ball mill for 10 hours to obtain the desired antifouling gel particles.

[0118] Example 4

[0119] The preparation method of the antifouling gel particles in this embodiment is as follows: The types and addition amounts of the raw materials in the preparation method are shown in Table 1:

[0120] S1. Preparation of graphene functional materials;

[0121] S2. Preparation of antifouling gel particles.

[0122] Step S1 includes the following steps:

[0123] S11, dissolving the isothiazolinone antifouling agent: adding the isothiazolinone antifouling agent into dimethyl sulfoxide solvent, stirring and dispersing into a 25%wt solution;

[0124] S12, graphene loaded with rare earth cerium / isothiazolinone antifouling agent: freeze-dry graphene oxide and evenly disperse it in anhydrous DMF, ultrasonically disperse it for 0.5h, then add acrylic isocyanate, stir and disperse it for 6h, then add rare earth cerium solution and isothiazolinone antifouling agent solution in sequence, and then ultrasonically disperse it for 5h, so that rare earth ions and isothiazolinone antifouling agent are adsorbed between graphene layers;

[0125] S13, washing and drying: After the reaction is completed, the precipitate is obtained by centrifugation, and washed with deionized water for 3 times. The precipitate is then vacuum dried at 120° C. for 2 h, crushed and ground into powder to obtain graphene functional material.

[0126] Step S2 includes the following steps:

[0127] S21, synthesis of free radical copolymer hydrophilic gel: add acrylamide monomer, acrylic acid monomer, graphene functional material, crosslinking agent, initiator and deionized water into a reactor, stir and heat to 80°C, add 0.5 parts of catalyst into the reactor after 10 minutes, continue stirring for 3 hours and then stop stirring, let stand at 20°C and continue to react for 1 hour to obtain gel;

[0128] S22, washing and drying: taking out the gel prepared in step S21, squeezing it into small pieces, washing it with deionized water for 3 times, drying it in an oven, and then grinding it in a high-energy ball mill for 10 hours to obtain the desired antifouling gel particles.

[0129] Performance Testing

[0130] (1) Algae inhibition effect of graphene functional materials

[0131] The algae inhibition effect of the graphene functional materials of Examples 1 to 4 was tested, and the testing method is as follows:

[0132] Take 10ml of the Chlorella solution cultured to the exponential growth phase and place it in a 250ml conical flask. Mix the functional materials to be tested in dimethyl sulfoxide (DMSO) which has low toxicity to organisms. Adjust the concentration to 5ppm by adding culture solution. Culture under the conditions of light intensity of about 3000lux, light-dark ratio of 12:12, and temperature of 20℃. Take out and shake for 5min every 24 hours. After 72h, detect the absorbance of the algae solution in the culture dish. Since the absorbance value is proportional to the algae concentration, convert the absorbance value into the algae solution concentration to calculate the death percentage of the algae.

[0133] Table 2 Algae inhibition efficiency of graphene functional materials

[0134]

[0135] The control group 1 was without any added substances, the control group 2 was added with graphene oxide alone, the control group 3 was added with graphene oxide and rare earth cerium solution, the control group 4 was added with graphene oxide and isothiazolinone antifouling agent, and the graphene functional materials prepared in Examples 1 to 4. It can be found from Table 2 that the control group 2 also had an antibacterial effect by adding graphene oxide alone, and the antibacterial efficiency could reach 38.6%; the control group 3 added graphene oxide and rare earth cerium solution with an antibacterial efficiency of 54.2%, the control group 4 added graphene oxide and isothiazolinone antifouling agent with an antibacterial efficiency of 76.4%, and the antibacterial efficiency of the graphene functional materials of Examples 1 to 4 was greatly improved compared with the control group, and the antibacterial efficiency was all above 87.7%, and the antibacterial efficiency of the graphene functional material of Example 4 was the highest at 90.4%.

[0136] (2) Antifouling gel’s antifouling performance

[0137] The antifouling performance of the invented antifouling gel was tested in real sea. The test method was carried out using the "Antifouling Paint Sample Shallow Sea Immersion Test Method", and the sample was made with reference to the formula in Example 2. A real sea hanging test was carried out in Dalipu Island, Xiamen. After 12 months of real sea immersion, it was found that there was no fouling organism attached to the surface of the antifouling gel, the paint film was intact, and there was no bubbling, cracking, or falling off, indicating that the invented antifouling gel has excellent antifouling and mechanical properties.

[0138] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the scope defined by the claims.

Claims

1. An antifouling gel particle, characterized in that: The antifouling gel particles include the following components in parts by weight: 10-20 parts of acrylamide monomer; 10-20 parts of acrylic acid-based monomer; 3-5 parts of graphene functional material; 0.1-0.5 parts of cross-linking agent; Initiator 0.2-0.7 parts; Catalyst 0.1-0.5 parts; 50-70 parts of deionized water; The graphene functional material comprises graphene oxide, rare earth cerium solution and isothiazolinone antifouling agent; the rare earth cerium solution and isothiazolinone antifouling agent solution are loaded on graphene oxide, and an acrylic acid double bond structure is grafted on the surface of the graphene oxide. The method for preparing the antifouling gel particles comprises the following steps: S1. Preparation of graphene functional materials; S2. Preparation of antifouling gel particles; Step S1 includes the following steps: S11, dissolving the isothiazolinone antifouling agent: adding the isothiazolinone antifouling agent into dimethyl sulfoxide solvent, stirring and dispersing into a 25%wt solution; S12, graphene loaded with rare earth cerium / isothiazolinone antifouling agent: freeze-dry graphene oxide and evenly disperse it in anhydrous DMF, and ultrasonically disperse it for 0.5h; then add acrylic isocyanate, and stir and react for 6h under nitrogen protection; then add rare earth cerium solution and isothiazolinone antifouling agent solution in sequence, and then ultrasonically disperse it for 2-5h, so that rare earth ions and isothiazolinone antifouling agent are adsorbed between graphene layers; S13, washing and drying: After the reaction is completed, the precipitate is obtained by centrifugation, and washed with deionized water for 2 to 3 times. The precipitate is then vacuum dried at 120° C. for 2 h, crushed and ground into powder to obtain graphene functional material.

2. The antifouling gel particle according to claim 1, characterized in that: The isothiazolinone antifouling agent is at least one of 2-methyl-4-isothiazoline-3-one, 4,5-dichloro-N-octyl-4-isothiazoline-3-one and 1,2-benzisothiazolin-3-one.

3. The antifouling gel particles according to claim 1, characterized in that: The rare earth cerium solution is at least one of cerium nitrate and cerium sulfate.

4. The antifouling gel particles according to claim 1, characterized in that: The acrylamide monomer is at least one of acrylamide, N-isopropylacrylamide and N-diethylacrylamide.

5. The antifouling gel particles according to claim 1, characterized in that: The acrylic monomer is at least one of acrylic acid, hydroxypropyl methacrylate and hydroxyethyl methacrylate.

6. The antifouling gel particles according to claim 1, characterized in that: The cross-linking agent is at least one of ethylene glycol dimethacrylate, N,N-methylenebisacrylamide, and oligoethylene glycol dimethacrylate.

7. The antifouling gel particles according to claim 1, characterized in that: The initiator is at least one of potassium persulfate, ammonium persulfate, azobisisobutylamidine hydrochloride, and VA044 initiator; the catalyst is at least one of tetramethylethylenediamine and tetramethylhexanediamine.

8. The antifouling gel particles according to claim 1, characterized in that: Step S2 includes the following steps: S21, synthesis of free radical copolymer hydrophilic gel: add acrylamide monomer, acrylic acid monomer, graphene functional material, crosslinking agent, initiator and deionized water into a reaction kettle, stir and heat to 60-80°C, add 0.1-0.5 parts of catalyst into the reaction kettle after 10 minutes, continue stirring for 2-3 hours and then stop stirring, let stand at 10-20°C and continue to react for 1 hour to obtain gel; S22, washing and drying: taking out the gel prepared in step S21, squeezing it into small pieces, washing it with deionized water for 2 to 3 times, drying it in an oven, and then grinding it in a high-energy ball mill for 10 hours to obtain the desired antifouling gel particles.

Images