Silane coupling agent containing selenonium ions, preparation method of silane coupling agent and application of silane coupling agent in marine antifouling

Abstract

The invention discloses a silane coupling agent containing selenonium ions as well as a preparation method and application of the silane coupling agent in marine antifouling, and the preparation method comprises the following steps: dispersing selenolactone into a solution containing amino siloxane and a catalyst, adding halogenated hydrocarbon, carrying out primary stirring reaction, filtering to obtain a crude product, and adding sulfonate, and carrying out secondary stirring reaction to obtain the silane coupling agent. The silane coupling agent containing selenonium ions is synthesized through a one-pot method, and the method is simple, convenient, environmentally friendly and high in efficiency. The silane coupling agent grease containing selenonium ions can show excellent antibacterial performance even under the condition of low addition amount as an antibacterial agent. Besides, the structure of selenonium ions adopts a form of a silane coupling agent, can independently form a film, effectively overcomes the problem of poor adhesiveness of organic silicon, and retains the characteristic of low surface energy of organic silicon, thereby effectively preventing adhesion of bacteria, seaweed and other marine microorganisms, and greatly improving the antifouling effect of the marine surface.

Description

Technical Field

[0001] The invention relates to a silane coupling agent containing selenium onium ions, a preparation method thereof and application of the silane coupling agent in marine antifouling, and belongs to the technical field of coatings. Background Art

[0002] Frequent contact between ships and marine engineering facilities causes marine organisms such as seaweed and shellfish to attach and form biofouling. These biofoulings not only increase the burden on the hull and reduce navigation efficiency, but may also cause damage to the marine ecological environment. Traditional antifouling methods such as the use of heavy metal coatings are effective in the short term, but in the long run they pose a serious threat to the environment and human health. Therefore, the development of environmentally friendly and efficient antifouling materials has become an important topic in the field of marine engineering.

[0003] Silicone resin is regarded as a potential environmentally friendly antifouling material due to its excellent weather resistance, water resistance and biocompatibility. Although traditional silicone resin coatings have been widely studied and applied in the field of marine antifouling due to their low surface energy characteristics, they have some obvious shortcomings. First, the mechanical strength and adhesion of pure silicone coatings are poor, which limits their durability and practicality in the marine environment. Secondly, the high curing temperature of silicone resin coatings leads to increased construction difficulty and increased energy consumption. In addition, silicone resin coatings have poor resistance to organic solvents and will become soft when encountering organic solvents such as gasoline, which affects their application in certain specific marine environments. In addition, although the antifouling performance of silicone coatings is good, the adhesion strength and mechanical properties of the coating film are poor, and an intermediate paint is needed to enhance the bonding strength between the antifouling paint and the anticorrosive primer, which not only increases the construction difficulty, but also the poor mechanical properties make the coating easily damaged by external forces and difficult to repair, reducing the service life of the coating. Finally, silicone antifouling coatings cannot completely inhibit the growth of fouling organisms on their surfaces, especially biofilms, and severe biofilms will greatly increase the resistance of ships to navigation. When using such coatings, the time a ship spends at a port must be strictly limited. Therefore, developing new silicone resin coatings to overcome the above shortcomings is of great significance for improving marine antifouling efficiency and protecting the marine environment. Summary of the invention

[0004] The purpose of the present invention is to provide a silane coupling agent containing selenonium ions, a preparation method thereof and an application in marine antifouling. The silane coupling agent containing selenonium ions can exhibit excellent antibacterial properties at a low addition amount as an antibacterial agent.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: A silane coupling agent containing selenium ions, having any of the following molecular structural formulas: , Among them, R1, R2, R3, R6, R7, R8, R9, R 10 , R 11 , R 14 , R 15 , R 16 Any of the following groups: -CH3, -O-(CH2) x -CH3, -O-(CH2) y -C(CH3)3, and R1, R2, R3, R6, R7, R8, R9, R 10 , R 11 , R 14 , R 15 , R 16 Not at the same time -CH3; R4, R 12 , R 13 , R 17 Straight chain alkyl-(CH2) with or without primary amine substituents z -; R5 is any of the following groups: -H, -Ph; Moreover, n=1-20, x=0-50, y=0-50, z=1-50 (n, x, y, z are all integers).

[0006] Preferably, n=any integer between 5-16.

[0007] The preparation method of the silane coupling agent containing selenium onium ions is to disperse selenol in a solution containing aminosiloxane and a catalyst, add halogenated hydrocarbons for a stirring reaction, filter to obtain a crude product, and then add sulfonate for a second stirring reaction.

[0008] Preferably, the aminosiloxane is one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, di(3-trimethoxysilylpropyl)amine, diethylenetriaminopropyltrimethoxysilane, diethylaminomethyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and 3-piperazinylpropylmethyldimethoxysilane.

[0009] Preferably, the catalyst is triethylamine or pyridine.

[0010] Preferably, the halogenated hydrocarbon is one or more of 1-bromodecane, 1-bromododecane, 1-bromodetetradecane and 1-bromodehexadecane.

[0011] Preferably, the sulfonate is one or more of methyl trifluorosulfonate, ethyl trifluoromethanesulfonate, phenyl trifluoromethanesulfonate and trifluoromethyl trifluoromethanesulfonate.

[0012] Preferably, the molar ratio of selenolactone, aminosilicone, catalyst, halogenated hydrocarbon and sulfonate is (15-30):(16-35):(5-15):(16-35):(15-30).

[0013] Preferably, the stirring reaction conditions are: room temperature, 15-40h; The conditions for the secondary stirring reaction are: room temperature, 20-50h.

[0014] Preferably, the filtration is carried out using alumina.

[0015] The application of any of the above-mentioned silane coupling agents containing selenium onium ions in marine antifouling is to use the silane coupling agent containing selenium onium ions as a coating antibacterial agent.

[0016] The beneficial effects of the present invention are: Selenium ions have the properties of antibacterial and catalytic dynamic exchange of siloxanes. When introduced into silicone coatings, they can be used as catalysts to achieve the exchange of siloxanes at room temperature without overflow and loss. Traditional silicone materials are easily damaged due to their own structure and properties. In contrast, the selenium ion-containing silicone resin provided in this application can solve the problem of silicone recoating and achieve self-repair of the coating. General fields of materials: surface anti-fouling protection for underwater facilities such as ships, marine engineering, offshore wind power, marine ranches, underwater ropes, underwater monitoring equipment, etc.; The selenium onium ion-containing silicone resin was synthesized by a one-pot method, which is not only simple, environmentally friendly, but also highly efficient. As an antibacterial agent, the selenium onium ion-containing silicone resin can exhibit excellent antibacterial properties even at low addition amounts. In addition, the structure of the selenium onium ion adopts the form of a silane coupling agent, which can form a film independently, effectively overcoming the problem of poor adhesion of silicone, while retaining the low surface energy characteristics of silicone, thereby effectively preventing the attachment of marine microorganisms such as bacteria and seaweed, greatly improving the antifouling effect on the ocean surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the H NMR spectrum of hexadecyl chain selenoether; Figure 2 This is the C NMR spectrum of hexadecyl chain selenoether; Figure 3 This is a partial enlarged view of the C NMR spectrum of hexadecyl chain selenoether; Figure 4 It is the hydrogen nuclear magnetic resonance spectrum of hexadecyl chain selenium ion silane coupling agent; Figure 5This is a comparison chart of the antibacterial properties of the prepared PDMS membranes containing different contents of hexadecyl chain selenium ion silane coupling agents; Figure 6 This is a comparison chart of the contact angle changes of the prepared PDMS films containing different contents of hexadecyl chain selenium ion silane coupling agent. DETAILED DESCRIPTION

[0018] The preparation principle of the selenonium ion-containing silane coupling agent in this embodiment is to open the amino-containing siloxane ring to form selenolactone, react with halogenated hydrocarbons of different chain lengths to obtain selenium ethers of different alkyl chains, and react the selenium ethers with methyl trifluorosulfonate to obtain the selenium ion-containing silane coupling agent. The reaction equation is as follows:

[0019] .

[0020] The specific preparation method is as follows.

[0021] Preparation of decanyl chain selenonium ion silane coupling agent: Weigh 3-aminopropyltrimethoxysilane (3.759 g, 21 mmol) and triethylamine (2.33 g, 10 mmol) in THF (10 mL) and add them to a flask equipped with a magnetic stirrer, weigh selenolactone (2.98 g, 20 mmol) and slowly add it to the flask, weigh 1-bromodecane (4.64 g, 21 mmol) and dissolve it in 10 mL THF and add it to the flask together, stir the solution at room temperature for 24 h, and track it with nuclear magnetic resonance; after the reaction is complete, filter out trimethylammonium bromide with neutral alumina to obtain a crude product, slowly add methyl trifluorosulfonate (3.28 g, 20 mmol) to the crude product while stirring at room temperature, and confirm the onium ionization with nuclear magnetic resonance. The above reaction route is as follows:

[0022] .

[0023] Preparation of dodecyl chain selenonium ion silane coupling agent: Weigh 3-aminopropyltrimethoxysilane (3.759 g, 21 mmol) and triethylamine (2.33 g, 10 mmol) in THF (10 mL) and add them to a flask equipped with a magnetic stirrer, weigh selenolactone (2.98 g, 20 mmol) and slowly add it to the flask, weigh 1-bromododecane (5.22 g, 21 mmol) and dissolve it in 10 mL THF and add it to the flask together, stir the solution at room temperature for 24 h, and track it with nuclear magnetic resonance; after the reaction is complete, filter out trimethylammonium bromide with neutral alumina to obtain a crude product, slowly add methyl trifluorosulfonate (3.28 g, 20 mmol) to the crude product while stirring at room temperature, and confirm the onium ionization with nuclear magnetic resonance. The above reaction route is as follows:

[0024] .

[0025] Preparation of tetradecyl chain selenonium ion silane coupling agent: Weigh 3-aminopropyltrimethoxysilane (3.759 g, 21 mmol) and triethylamine (2.33 g, 10 mmol) in THF (10 mL) and add them to a flask equipped with a magnetic stirrer, weigh selenolactone (2.98 g, 20 mmol) and slowly add it to the flask, weigh 1-bromotetradecane (5.82 g, 21 mmol) and dissolve it in 10 mL THF and add it to the flask together, stir the solution at room temperature for 24 h, and track it with nuclear magnetic resonance; after the reaction is complete, filter out trimethylammonium bromide with neutral alumina to obtain a crude product, slowly add methyl trifluorosulfonate (3.28 g, 20 mmol) to the obtained crude product while stirring at room temperature, and confirm the onium ionization with nuclear magnetic resonance. The above reaction route is as follows:

[0026] .

[0027] Preparation of hexadecyl chain selenonium ion silane coupling agent: Weigh 3-aminopropyltrimethoxysilane (3.759 g, 21 mmol) and triethylamine (2.33 g, 10 mmol) in THF (10 mL) and add them to a flask equipped with a magnetic stirrer. Weigh selenolactone (2.98 g, 20 mmol) and slowly add it to the flask. Weigh 1-bromohexadecane (6.40 g, 21 mmol) and dissolve it in 10 mL THF and add them to the flask together. Stir the solution at room temperature for 24 h and follow the NMR (H NMR spectrum as shown in Figure 2). Figure 1 As shown, the carbon NMR spectrum is Figure 2 ,3 After the reaction is complete, trimethylammonium bromide is filtered out with neutral alumina to obtain a crude product. Methyl trifluorosulfonate (3.28 g, 20 mmol) is slowly added to the crude product while stirring at room temperature. The onium ionization is confirmed by NMR (H NMR spectrum as shown in Figure 4 The above reaction route is as follows:

[0028] .

[0029] Taking hexadecyl selenium ion silane coupling agent as an example, the PDMS membrane (denoted as A) to which different contents of hexadecyl selenium ion silane coupling agent as antibacterial agent (1%-10%, the content is calculated according to the mass ratio of hexadecyl selenium ion silane coupling agent to PDMS) were added. 16 Se + x -PDMS, x represents the content of hexadecyl chain selenonium ion silane coupling agent), PDMS membrane without selenonium ion silane coupling agent as antibacterial agent (denoted as PDMS) and blank control group (denoted as Control) were tested for their antibacterial properties. The membrane preparation method was as follows: PDMS (5 g), TEOS (0.25 g) and DBTDL (0.25 g) were weighed in a beaker, hexadecyl chain selenonium ion silane coupling agent was added, dissolved with 5 mL CH3Cl and stirred rapidly to mix evenly, then poured into a mold, the solvent was drained and then cured to form a film.

[0030] The test method is as follows: use a pipette to take a certain amount of LB culture medium into a centrifuge tube, mark it with S and E, take out the bacteria from the refrigerator, pick a little into the centrifuge tube, and place it in a shaker for shaking (16-22 hours for S bacteria (Staphylococcus aureus), and no more than 15 hours for E bacteria (Escherichia coli)). Take it out when the bacterial solution becomes turbid, put it in the refrigerator, take out the cultured bacteria, adjust the S and E bacteria to OD = 0.09 and 0.08 respectively with an enzyme marker, take 10μL of the bacterial solution and add 1mL LB. Cut the film to an appropriate size and put it into a well plate. Take 10 μL of the 100-fold diluted bacterial solution and drop it on the membrane. Incubate it in a wet box for 24 h. After incubation, add 2 mL of PBS to the well plate and shake it gently to mix it evenly. Take 10 μL of the sample to be tested and drop it into the agar plate three times each time. Rotate the agar plate while smearing it with a triangular spreading stick. After coating, place the agar plate upside down in a constant temperature and humidity oven (15 h for E bacteria and 20-24 h for S bacteria) and observe the results.

[0031] Antibacterial results such as Figure 5As shown in the figure, the antibacterial results show that PDMS and the Control group have almost no antibacterial properties, and the antibacterial efficiency is close to 0. However, with the increase in the amount of hexadecyl chain selenium ion silane coupling agent added, the antibacterial efficiency is greatly improved. When the addition amount reaches 1%, it has a good antibacterial effect on S bacteria; when the addition amount reaches 2.5%, it also has a good antibacterial effect on E bacteria.

[0032] Comparison of water contact angles of PDMS membranes with different contents of hexadecyl selenium ion silane coupling agent added. Figure 6 As shown, the water contact angle of PDMS is 97.5°. When the addition amount of hexadecyl chain selenonium ion silane coupling agent reaches 1%, the contact angle is 102.8°, when the addition amount reaches 2.5%, the contact angle is 97.3°, when the addition amount reaches 5%, the contact angle is 101.3°, when the addition amount reaches 10%, the contact angle is 100.5°, when the addition amount reaches 20%, the contact angle is 103.0°. The data show that the introduction of selenium ions in PDMS has little effect on its contact angle, and they are all greater than 90°, which is hydrophobic.

[0033] The sulfonium ion-containing silane coupling agent provided in the present application can also be combined with resins, pigments, fillers, additives, etc. to form a coating composition that can be applied to the surface of underwater marine components to prevent the attachment and growth of marine organisms.

[0034] The above is only a preferred implementation of the patent of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the patent of the present invention. These improvements and modifications should also be regarded as the protection scope of the patent of the present invention.

Claims

1. A silane coupling agent containing selenium ions, characterized in that: Having any of the following molecular structures: ， Among them, R1, R2, R3, R6, R7, R8, R9, R 10 , R 11 , R 14 , R 15 , R 16 Any of the following groups: -CH3, -O-(CH2) x -CH3, -O-(CH2) y -C(CH3)3, and R1, R2, R3, R6, R7, R8, R9, R 10 , R 11 , R 14 , R 15 , R 16 Not at the same time -CH3; R4, R 12 , R 13 , R 17 Straight chain alkyl-(CH2) with or without primary amine substituents z -; R5 is any of the following groups: -H, -Ph; And, n=1-20, x=0-50, y=0-50, z=1-50.

2. The silane coupling agent containing selenonium ions according to claim 1, characterized in that: n=any integer between 5 and 16.

3. The method for preparing a silane coupling agent containing selenonium ions according to any one of claims 1 to 2, characterized in that: The method comprises dispersing selenol in a solution containing aminosiloxane and a catalyst, adding halogenated hydrocarbon, stirring and reacting once, filtering to obtain a crude product, and then adding sulfonic acid ester, stirring and reacting for a second time.

4. The method for preparing a silane coupling agent containing selenonium ions according to claim 3, characterized in that: The aminosiloxane is one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, di(3-trimethoxysilylpropyl)amine, diethylenetriaminopropyltrimethoxysilane, diethylaminomethyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and 3-piperazinylpropylmethyldimethoxysilane.

5. The method for preparing a silane coupling agent containing selenium onium ions according to claim 3, characterized in that: The catalyst is triethylamine or pyridine.

6. The method for preparing a silane coupling agent containing selenonium ions according to claim 3, characterized in that: The halogenated hydrocarbon is one or more of 1-bromodecane, 1-bromododecane, 1-bromodetetradecane and 1-bromodehexadecane.

7. The method for preparing a silane coupling agent containing selenium onium ions according to claim 3, characterized in that: The sulfonate ester is one or more of methyl trifluorosulfonate, ethyl trifluoromethanesulfonate, phenyl trifluoromethanesulfonate and trifluoromethyl trifluoromethanesulfonate.

8. The method for preparing a silane coupling agent containing selenium ions according to claim 3, characterized in that: The molar ratio of selenol, aminosiloxane, catalyst, halogenated hydrocarbon and sulfonate is (15-30):(16-35):(5-15):(16-35):(15-30).

9. The method for preparing a silane coupling agent containing selenonium ions according to claim 3, characterized in that: The conditions for the primary stirring reaction are: room temperature, 15-40h; The conditions for the secondary stirring reaction are: room temperature, 20-50h.

10. Use of the selenonium ion-containing silane coupling agent according to any one of claims 1 to 2 in marine antifouling, characterized in that: The invention relates to using a silane coupling agent containing selenium onium ions as a coating antibacterial agent.

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