Marine antifouling coating prepared by hybrid copolymerization of epoxy, acrylate and elemental sulfur
Marine antifouling coatings were prepared by anionic hybrid copolymerization of elemental sulfur, epoxy, and acrylate esters catalyzed by alkali, which solved the problem of the fragile mechanical properties of traditional epoxy coatings in marine environments and improved self-healing and antibacterial effects.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHANGZHOU UNIV
- Filing Date
- 2024-06-12
- Publication Date
- 2026-05-19
AI Technical Summary
Traditional epoxy coatings are mechanically fragile in marine environments, with poor flexibility and impact resistance, and cannot meet the requirements for corrosion and wear resistance.
Marine antifouling coatings are prepared by anionic hybrid copolymerization of elemental sulfur with binary or multi-component epoxy and acrylate containing silicon groups via alkali catalysis. The thermodynamic properties of the polymer are adjusted and antibacterial and self-healing functions are introduced.
It achieves self-healing and self-polishing properties of epoxy coatings, reducing costs while improving antibacterial effects and mechanical properties, making it suitable for marine environments.
Smart Images
Figure CN118546603B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer synthesis, specifically relating to a marine antifouling coating prepared by hybrid copolymerization of epoxy, acrylate and elemental sulfur. Background Technology
[0002] The ocean is rich in resources and energy, but the development of these resources inevitably leads to the problem of marine biofouling. In applications such as marine engineering equipment and vessels, crude oil pipelines, and chemical production reactors, the corrosion and abrasion of substrates are severe, placing high demands on the corrosion resistance and abrasion resistance of anti-corrosion coatings.
[0003] Epoxy resins are widely used in protective coatings due to their excellent mechanical properties, chemical stability, and resistance to ion penetration. The mechanical properties of traditional epoxy coatings are directly related to the resin itself; they have high strength after curing, but are brittle, lack flexibility and impact resistance, and have limited functionality, failing to meet the protective requirements of special and extreme service environments. Summary of the Invention
[0004] This invention addresses the shortcomings of existing epoxy resin coatings by providing a marine antifouling coating. The marine antifouling coating is prepared by anionic hybrid copolymerization of elemental sulfur, binary or multi-component epoxy resins, and acrylates containing silicon groups via alkali catalysis. The specific synthesis process is as follows: Under normal pressure, elemental sulfur, binary or multi-component epoxy resins, acrylates containing silicon groups, and a solvent are added to a flask. An alkali catalyst is added, and polymerization is carried out at 30–100°C for 1–12 hours. After polymerization, the mixture is cooled and diluted with an equal volume of solvent.
[0005] The base catalyst can be an organic base or an inorganic base catalyst.
[0006] The binary or multi-component epoxy compounds are: bisphenol A diglycidyl ether, epoxidized soybean oil, triglyceride glycidyl ether, ethylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, polycaprolactone diglycidyl ether, or one or more of these compounds.
[0007] The acrylate containing a silicon group is one or more of the following: 3-(trimethoxysilane)acrylate, 3-(trimethoxysilane)methacrylate, triisopropylsilyl acrylate, triisopropylsilyl methacrylate, acryloyloxypropyltriethoxysilane, methacryloyloxypropyltriethoxysilane, and acrylate-terminated polysiloxanes.
[0008] The composition of marine antifouling coatings according to the molar ratio of monomer groups is: elemental sulfur: epoxy (binary or multi-component): acrylate (containing silicon groups): catalyst = (40-160): (20-120): (40-160): (1-5).
[0009] The preferred composition of marine antifouling coating according to the molar ratio of monomer groups is: elemental sulfur: epoxy (binary or multi-component): acrylate (containing silicon groups): catalyst = (40-80): (40-80): (80-160): (1-2).
[0010] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0011] (1) This invention uses elemental sulfur, epoxy, and acrylate as raw materials to obtain ternary random copolymers through anionic hybrid copolymerization. The thermodynamic properties of the polymer can be adjusted by regulating the structure and ratio of the epoxy monomers, and the polymer can also be functionalized by using acrylates with different functional groups.
[0012] (2) Elemental sulfur has long been considered an antibacterial agent, used orally to treat bacterial infections and topically to treat skin infections. It is also important in preventing biofilm formation. This invention introduces elemental sulfur to give the coating an intrinsic antibacterial effect without the need for additional antifouling agents, preserving polymer properties while reducing costs.
[0013] (3) The introduction of elemental sulfur in this invention enables the coating to have a self-healing function. The ring-opening reaction of elemental sulfur allows a large number of sulfur and polysulfide segments in the polymer to undergo dynamic exchange at a lower temperature, resulting in polymer chain recombination and self-repair.
[0014] (4) Trialkylsilyl (meth)acrylate copolymers have stable hydrolysis rates and self-smoothing properties. In this invention, the acrylates containing silicon groups can be hydrolyzed in seawater, giving the coating self-polishing properties. Attached Figure Description
[0015] Figure 1 The infrared spectrum of the polymer product in Example 17 is shown.
[0016] Figure 2 The GPC curve of the product obtained in Example 17 is shown.
[0017] Figure 3 The image shows the XRD curve of the product obtained in Example 17.
[0018] Figure 4 The XPS curve of the product obtained in Example 17 is shown.
[0019] Figure 5 DSC curves of the products obtained from steps 9, 10, and 17.
[0020] Figure 6 The TG curves are for the products obtained in Examples 9, 10, and 17.
[0021] Figure 7The adhesion strength of the products obtained in Examples 9, 10, and 17.
[0022] Figure 8 The contact angle is the product obtained in Examples 9, 10, and 17.
[0023] Figure 9 The hardness of the products obtained in Examples 9, 10, and 17 is given.
[0024] Figure 10 The degradation performance of the product obtained in Example 17 is shown.
[0025] Figure 11 Fluorescence micrographs of bacterial adhesion on the coating of the product obtained in Example 17 after different days.
[0026] Figure 12 The self-healing performance of the product obtained in Example 17 is shown in the three images above (the top three images are SEM images before self-healing, and the bottom three images are SEM images after self-healing). Detailed Implementation
[0027] The present invention will be further described below with reference to the embodiments, but it is not limited to the following embodiments. For process parameters not specifically noted, conventional techniques can be referred to.
[0028] Example 1
[0029] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 11.70 mL of triisopropylsilyl acrylate, 3.00 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.20 mL of DBU dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0030] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to obtain a red solid. The yield of the obtained product was 90%, and the molecular weight was M. w =16830 g / mol, molecular weight distribution is 3.11.
[0031] Example 2
[0032] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 11.70 mL of triisopropylsilyl acrylate, 1.50 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.20 mL of DBU dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0033] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 84%, and the molecular weight was M. w =15320 g / mol, molecular weight distribution is 2.51.
[0034] Example 3
[0035] Add a magnetic rotor to a 250 mL flask, then add bisphenol A diglycidyl ether (4.01 mL), triisopropylsilyl acrylate (11.70 mL), elemental sulfur (3.00 g), and tetrahydrofuran (30 mL). Stir to disperse evenly, then add DBU (0.20 mL) dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0036] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to obtain a red solid. The yield of the obtained product was 94%, and the molecular weight was M. w =16230 g / mol, molecular weight distribution is 2.64.
[0037] Example 4
[0038] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 16.40 mL of triisopropylsilyl acrylate, 3.00 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.20 mL of DBU dropwise; polymerize at 30 °C for 12 h, and after polymerization, cool and dilute with an equal volume of solvent.
[0039] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 91%, and the molecular weight was M. w =14203 g / mol, molecular weight distribution is 2.61.
[0040] Example 5
[0041] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 11.70 mL of triisopropylsilyl acrylate, 3 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.10 mL of DBU dropwise; polymerize at 30 °C for 12 h, and after polymerization, cool and dilute with an equal volume of solvent.
[0042] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 85%, and the molecular weight was M. w =13650 g / mol, molecular weight distribution is 2.78.
[0043] Example 6
[0044] Add a magnetic rotor to a 250 mL flask, then add 7.4 mL of bisphenol A diglycidyl ether, 20 mL of triisopropylsilyl acrylate, 10 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.20 mL of DBU dropwise; polymerize at 30 °C for 12 h, and after polymerization, cool and dilute with an equal volume of solvent.
[0045] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 85%, and the molecular weight was M. w =15320 g / mol, molecular weight distribution is 2.51.
[0046] Example 7
[0047] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 11.70 mL of triisopropylsilyl acrylate, 3.00 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.20 mL of TDB dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0048] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 86%, and the molecular weight was M. w =14250g / mol, molecular weight distribution is 2.54.
[0049] Example 8
[0050] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 11.70 mL of triisopropylsilyl acrylate, 3.00 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.52 g of NaOH dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0051] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 84%, and the molecular weight was M. w =17430 g / mol, molecular weight distribution is 2.87.
[0052] Example 9
[0053] Add a magnetic rotor to a 250 mL flask, then add epoxidized soybean oil (7.62 mL), triisopropylsilyl acrylate (11.70 mL), elemental sulfur (3.00 g), and tetrahydrofuran (30 mL). Stir to disperse evenly, then add DBU (0.20 mL) dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0054] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to obtain a red solid. The yield of the obtained product was 81%, and the molecular weight was M. w =14631 g / mol, molecular weight distribution 2.87. The product was characterized using differential scanning calorimetry and thermogravimetric analysis, with results as follows: Figure 5 and 6 As shown. Simultaneously, the contact angle, adhesion strength, and hardness of the coating were tested, and the results are as follows. Figure 7 , Figure 8 and Figure 9 As shown.
[0055] Example 10
[0056] Add a magnetic rotor to a 250 mL flask, then add triglyceride glycidyl ether (3.20 mL), triisopropylsilyl acrylate (11.70 mL), elemental sulfur (3.00 g), and tetrahydrofuran (30 mL). Stir to disperse evenly, then add DBU (0.20 mL) dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0057] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 84%, and the molecular weight was M. w =13651 g / mol, molecular weight distribution 2.75. The product was characterized using differential scanning calorimetry and thermogravimetric analysis, with results as follows: Figure 5 and 6 As shown. Simultaneously, the contact angle, adhesion strength, and hardness of the coating were tested, and the results are as follows. Figure 7 , Figure 8 and Figure 9 As shown.
[0058] Example 11
[0059] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 12.20 mL of triisopropylsilyl methacrylate, 3.00 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.20 mL of DBU dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0060] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 86%, and the molecular weight was M. w =14561 g / mol, molecular weight distribution is 2.36.
[0061] Example 12
[0062] Add a magnetic rotor to a 250 mL flask, then add ethylene glycol diglycidyl ether (11.36 mL), triisopropylsilyl acrylate (11.70 mL), elemental sulfur (3.00 g), and tetrahydrofuran (30 mL). Stir to disperse evenly, then add DBU (0.20 mL) dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0063] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 84%, and the molecular weight was M. w =15610 g / mol, molecular weight distribution is 2.81.
[0064] Example 13
[0065] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 10.50 mL of 3-(trimethoxysilane)acrylate, 3.00 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.20 mL of DBU dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0066] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 86%, and the molecular weight was M. w =16532 g / mol, molecular weight distribution is 3.10.
[0067] Example 14
[0068] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 12.70 mL of methacryloxypropyltriethoxysilane, 3.00 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.20 mL of DBU dropwise; polymerize at 30 °C for 12 h. After polymerization, cool and dilute with an equal volume of solvent.
[0069] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 86%, and the molecular weight was M. w =15460 g / mol, molecular weight distribution is 2.54.
[0070] Example 15
[0071] Add a magnetic rotor to a 250 mL flask, then add bisphenol A diglycidyl ether (8.01 mL), triisopropylsilyl acrylate (11.70 mL), elemental sulfur (3.00 g), and tetrahydrofuran (30 mL). Stir to disperse evenly, then add DBU (0.20 mL) dropwise; polymerize at 80 °C for 4 h. After polymerization, cool and dilute with an equal volume of solvent.
[0072] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to obtain a red solid. The yield of the obtained product was 95%, and the molecular weight was M. w =14500g / mol, molecular weight distribution is 2.81.
[0073] Example 16
[0074] Add a magnetic rotor to a 250 mL flask, then add 8.01 mL of bisphenol A diglycidyl ether, 11.70 mL of triisopropylsilyl acrylate, 3.00 g of elemental sulfur, and 30 mL of tetrahydrofuran. Stir to disperse evenly, then add 0.20 mL of DBU dropwise; polymerize at 100 °C for 2 h. After polymerization, cool and dilute with an equal volume of solvent.
[0075] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to give a red solid. The yield of the obtained product was 91%, and the molecular weight was M. w =17623 g / mol, molecular weight distribution is 3.02.
[0076] Example 17
[0077] A magnetic rotor was added to a 250 mL flask, along with 8.01 mL of bisphenol A diglycidyl ether, 11.70 mL of triisopropylsilyl acrylate, 3.00 g of elemental sulfur, and 30 mL of tetrahydrofuran. The mixture was stirred until homogeneous, and then 0.20 mL of DBU was added dropwise. Polymerization was carried out at 60 °C for 6 hours, after which the reaction was complete.
[0078] Post-processing: After stopping the reaction, the product was precipitated in methanol, the solvent was poured off, and the product was dried to obtain a red solid. The yield of the obtained product was 94%. The polymer was characterized by infrared spectroscopy and gel permeation chromatography, and the results are as follows: Figure 1 and 2 As shown. Molecular weight M w =14530 g / mol, molecular weight distribution is 2.63.
[0079] The product was characterized using X-ray diffraction and X-ray photoelectron spectroscopy, and the results are as follows: Figure 2 and3 As shown.
[0080] The products were characterized using differential scanning calorimetry and thermogravimetric analysis, and the results are as follows: Figure 5 and 6 As shown.
[0081] Simultaneously, the contact angle and adhesion strength of the coating were tested, and the results are as follows: Figure 7 and Figure 8 As shown.
[0082] The obtained coating was applied to a glass plate and hydrolysis experiments were conducted under different conditions. The results are as follows: Figure 9 As shown.
[0083] The obtained coating was immersed in artificial seawater to test its antibacterial properties, and the results were as follows: Figure 10 As shown;
[0084] The paint surface was scratched with a blade, and after being placed at 30°C for 48 hours, the cracked areas were observed using SEM. The results are as follows. Figure 11 As shown.
Claims
1. A marine antifouling coating, characterized in that, The marine antifouling coating is composed of the following monomer group molar ratio: elemental sulfur: binary or multi-component epoxy: acrylate containing silicon groups: alkaline catalyst = 40-160: 20-120: 40-160: 1-5, and solvent; The acrylates containing silicon groups are: 3-(trimethoxysilane) acrylate, 3-(trimethoxysilane) methacrylate, triisopropylsilyl acrylate, triisopropylsilyl methacrylate, acryloyloxypropyltriethoxysilane, methacryloyloxypropyltriethoxysilane, and acrylate-terminated polysiloxanes.
2. The marine antifouling coating according to claim 1, characterized in that, The binary or multi-component epoxy is: bisphenol A diglycidyl ether, epoxidized soybean oil, triglyceride glycidyl ether, ethylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, polycaprolactone diglycidyl ether.
3. The marine antifouling coating according to claim 1, characterized in that, The marine antifouling coating is composed of the following monomer group molar ratio: elemental sulfur: binary or multi-component epoxy: acrylate containing silicon groups: alkaline catalyst = 40-80: 40-80: 80-160: (1-2), and solvent.
4. The marine antifouling coating according to claim 1, characterized in that, The alkaline catalyst is an organic or inorganic base.
5. The marine antifouling coating according to claim 1, characterized in that, The synthesis method of the marine antifouling coating is as follows: under normal pressure, elemental sulfur, binary or multi-component epoxy, acrylate containing silicon groups and solvent are added to a flask, an alkaline catalyst is added, and the polymerization reaction is carried out at 30-100℃ for 1-12 hours. After polymerization, the mixture is cooled and diluted with solvent.