Preparation method of benzothiazole-containing two-component organosilicon polyurea antifouling coating
By building a molecular network of all urea bond connections and introducing aminobenzothiazole antibacterial derivatives, the weak adhesion and impact resistance of silicone modified polyurea coatings in marine applications are solved, and high-strength and antibacterial coatings are achieved, with excellent antifouling properties.
Patent Information
- Application Number
- CN202510519220.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-24
- Publication Date
- 2025-07-04
AI Technical Summary
The existing silicone modified polyurea/polyurethane low-surface energy antifouling coatings have weak adhesion and poor impact resistance in marine applications, and traditional polymerization processes are difficult to achieve a coordinated improvement in the mechanical strength and antifouling performance of the coating. At the same time, the addition of antibacterial agents will lead to a decrease in mechanical properties.
By building a molecular network of all urea bonds, the aminobenzothiazole antibacterial derivatives are introduced to regulate the molecular chain structure of the polymer, and aminopropyl bi-terminated polydimethylsiloxane, polyetheramine and isocyanate are used as the main raw materials to form a high-strength silicone polyurea antifouling coating.
It achieves a balance between high mechanical properties and antibacterial properties, and the coating has excellent static antifouling capabilities and wide application potential.
Smart Images
Figure CN120248745A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of marine antifouling materials, and particularly to a high-strength silicone polyurea antifouling coating crosslinked by urea bonds and a preparation method thereof. By embedding thiazole antibacterial derivative molecules into the silicone system and constructing a single urea bond crosslinked network, the coating has both high mechanical strength and long-term antibacterial function, and can achieve efficient application in marine antifouling. Background Art
[0002] In the natural environment, there are various pollutants that have an adverse impact on human life. Especially in the marine field, the pollution problem is particularly prominent, covering various pollutants such as inorganic substances, organic substances, organisms, and composite fouling. Marine biofouling refers to the continuous growth and reproduction of a large number of fouling organisms on the surface of artificial underwater facilities. Marine antifouling coating technology is a research direction that has received much attention and is favored for its excellent low surface energy and smooth hydrophobic properties. Especially silicone-modified polyurea / polyurethane low surface energy coatings. This type of coating exhibits excellent anti-bioadhesion and excellent fouling release performance, and has become a widely studied and highly practical solution. At present, silicone-modified polyurea / polyurethane low surface energy antifouling coatings use polydimethylsiloxane (PDMS) as the matrix material. Although the fouling release function is achieved through the low surface energy characteristics, its weak adhesion force to the substrate interface (peel strength < 1.5 N / cm), poor impact resistance (elastic modulus < 5 MPa) and other defects significantly restrict its practical application (Kavanagh C J, Swain G W, Kovach B S, et al. The effects of silicone fluid additives and silicone elastomer matrices on barnacle adhesion strength [J]. Biofouling, 2003, 19(6): 381-390.). Introducing methyl methacrylate-ε-caprolactone copolymer can adjust the thermodynamic properties of the material (Yang H, Yao H, Feng K, et al. Revisiting the structure of copolymer via anionic hybrid copolymerization of methyl methacrylate and ε-caprolactone [J]. Polymer, 2022, 260: 125340.), but traditional polymerization processes are difficult to achieve a structurally regular organic / inorganic hybrid system, resulting in difficulty in synergistically improving the mechanical strength and antifouling performance of the coating.
[0003] In recent years, the research on new high-strength materials of silicone-modified polyurea with superior mechanical properties has been widely concerned. However, most of the new high-strength marine antifouling coatings now always need to rely on external antibacterial agents to achieve their antibacterial properties, which will cause their mechanical properties to be greatly reduced, resulting in a contradiction between mechanical properties and antibacterial properties (Sun J, Liu C, Duan J, et al. Facile fabrication of self-healing silicone-based poly (urea-thiourea) / tannic acid composite for anti-biofouling [J]. Journal of Materials Science & Technology, 2022, 124 (29): 1-13). Therefore, making the material have both high mechanical properties and good antibacterial properties is the trend and direction of the development of a new generation of high-strength marine antifouling coating materials. Summary of the invention
[0004] Based on the related problems existing in the background technology, the polymer molecular chain structure can be adjusted, aminopropyl dicapped polydimethylsiloxane (APT-PDMS, Mn = 1000g / mol), polyetheramine (D-400) as soft segments, dicyclohexylmethane-4,4-diisocyanate (HMDI) and hexamethylene diisocyanate (HDI) as hard segments, and 2-aminobenzothiazole (BIT) is introduced into the polymer main chain by chemical grafting to form a molecular network connected by all urea bonds, so as to comprehensively improve the mechanical properties and static antifouling ability of the material. A two-component silicone polyurea antifouling coating containing benzothiazole prepared by the present invention.
[0005] The specific steps are as follows:
[0006] (1) 0.38-2.24 g of dicyclohexylmethane-4,4-diisocyanate (HMDI) and 0.323-1.023 g of hexamethylene diisocyanate (HDI) were fully dissolved in 20 mL of tetrahydrofuran (THF), and the solution was then transferred to a three-necked round-bottom flask.
[0007] (2) 2.46-7.54 g of aminopropyl di-terminated polydimethylsiloxane (APT-PDMS) and 0.48-1.92 g of polyetheramine (D-400) were fully dissolved in 20 mL of tetrahydrofuran (THF).
[0008] (3) Then transfer the solution in Step 1 to a constant-pressure funnel connected to a three-necked round-bottom flask, and slowly drip it into the mixed solution of aminopropyl-terminated polydimethylsiloxane (APT-PDMS) and polyetheramine (D-400) in Step (2). Stir for 2 to 6 hours under a nitrogen atmosphere at a reaction temperature of 45 °C.
[0009] (4) Subsequently, raise the temperature to 60 °C, add 0.135 - 0.465 g of 2-aminobenzothiazole (BIT) to the precursor solution, and stir the mixture for 3 h.
[0010] Preferably according to the present invention, in Step (1), the dosage range of dicyclohexylmethane-4,4-diisocyanate (HMDI) is 0.38 - 2.24 g, and preferably 1.31 g.
[0011] Preferably according to the present invention, in Step (1), the dosage range of hexamethylene diisocyanate (HDI) is 0.323 - 1.023 g, and preferably 0.673 g.
[0012] Preferably according to the present invention, in Step (2), the dosage range of aminopropyl-terminated polydimethylsiloxane (APT-PDMS) is 2.46 - 7.54 g, and preferably 5.00 g.
[0013] Preferably according to the present invention, in Step (2), the dosage range of polyetheramine (D-400) is 0.48 - 1.92 g, and preferably 1.2 g.
[0014] Preferably according to the present invention, in Step (3), stir for 2 to 6 hours under a nitrogen atmosphere, and preferably for 4 hours.
[0015] Preferably according to the present invention, in Step (4), the dosage range of 2-aminobenzothiazole (BIT) is 0.135 - 0.465 g, and preferably 0.3 g.
[0016] The technical advantages of the present invention are as follows:
[0017] (1) The present invention constructs a single urea bond as the binding group, and directly introduces a thiazole derivative with excellent antibacterial effect into the traditional silicone system, so that the prepared benzothiazole-containing two-component silicone polyurea antifouling coating has excellent mechanical properties and good antibacterial properties, and can realize the wide application of this coating.
[0018] (2) The present invention can adjust the ratio of hard and soft segments in the polymer molecular chain by adjusting the ratio of isocyanate to benzothiazole, so as to obtain a marine antifouling coating with high mechanical properties. Brief Description of the Drawings
[0019] Figure 1This is the infrared spectrum of the benzothiazole-containing two-component silicone polyurea antifouling coating (film) prepared in Example 2 of the present invention.
[0020] Figure 2 This is the appearance diagram of the benzothiazole-containing two-component silicone polyurea antifouling coating (film) prepared in Example 2 of the present invention.
[0021] Figure 3 This is the water contact angle diagram of the benzothiazole-containing two-component silicone polyurea antifouling coating (film) prepared in Example 2 of the present invention.
[0022] Figure 4 This is the stress-strain curve of the benzothiazole-containing two-component silicone polyurea antifouling coating (film) prepared in Example 2 of the present invention and the coatings (films) prepared in Example 1, Example 3, Example 4 and Comparative Example 1.
[0023] Figure 5 This is the antibacterial test diagram of the benzothiazole-containing two-component silicone polyurea antifouling coating (film) prepared in Example 2 of the present invention and the coating prepared in Comparative Example 1.
[0024] Figure 6 This is the adhesion strength of the benzothiazole-containing two-component silicone polyurea antifouling coating (film) prepared in Example 2 of the present invention and the coatings (films) prepared in Example 1, Example 3, Example 4 and Comparative Example 1 on Q235 carbon steel plate and glass fiber-reinforced epoxy resin plate (GFE), respectively. Detailed implementation mode
[0025] The present invention will be further described below in conjunction with specific embodiments and drawings, but not limited thereto.
[0026] Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are all commercially available unless otherwise specified.
[0027] Example 1:
[0028] 1.31 g of HMDI and 0.589 g of HDI were fully dissolved in 20 mL of THF, and then the solution was transferred to a three-necked round-bottom flask. 5.00 g of APT-PDMS and 1.20 g of D-400 were fully dissolved in 20 mL of THF, and then the solution was transferred to a constant-pressure funnel connected to the three-necked round-bottom flask. The mixed solution of APT-PDMS and D-400 was slowly dropped in, and stirred for 4 hours under a nitrogen atmosphere at a reaction temperature of 45 °C. Subsequently, the temperature was raised to 60 °C, 0.15 g of BIT was added to the precursor solution, and the mixture was stirred for 3 h to finally obtain PDMHB-1.
[0029] Example 2:
[0030] 1.31 g of HMDI and 0.673 g of HDI were fully dissolved in 20 mL of THF, and then the solution was transferred to a three-necked round-bottom flask. 5.00 g of APT-PDMS and 1.20 g of D-400 were fully dissolved in 20 mL of THF, and then the solution was transferred to a constant-pressure funnel connected to the three-necked round-bottom flask. The mixed solution of APT-PDMS and D-400 was slowly dropped in, and the mixture was stirred for 4 hours under a nitrogen atmosphere at a reaction temperature of 45 °C. Subsequently, the temperature was raised to 60 °C, 0.3 g of BIT was added to the precursor solution, and the mixture was stirred for 3 h to finally obtain PDMHB-2.
[0031] Example 3:
[0032] 1.31 g of HMDI and 0.757 g of HDI were fully dissolved in 20 mL of THF, and then the solution was transferred to a three-necked round-bottom flask. 5.00 g of APT-PDMS and 1.20 g of D-400 were fully dissolved in 20 mL of THF, and then the solution was transferred to a constant-pressure funnel connected to the three-necked round-bottom flask. The mixed solution of APT-PDMS and D-400 was slowly dropped in, and the mixture was stirred for 4 hours under a nitrogen atmosphere at a reaction temperature of 45 °C. Subsequently, the temperature was raised to 60 °C, 0.45 g of BIT was added to the precursor solution, and the mixture was stirred for 3 h to finally obtain PDMHB-3.
[0033] Example 4:
[0034] 1.31 g of HMDI and 0.841 g of HDI were fully dissolved in 20 mL of THF, and then the solution was transferred to a three-necked round-bottom flask. 5.00 g of APT-PDMS and 1.20 g of D-400 were fully dissolved in 20 mL of THF, and then the solution was transferred to a constant-pressure funnel connected to the three-necked round-bottom flask. The mixed solution of APT-PDMS and D-400 was slowly dropped in, and the mixture was stirred for 4 hours under a nitrogen atmosphere at a reaction temperature of 45 °C. Subsequently, the temperature was raised to 60 °C, 0.6 g of BIT was added to the precursor solution, and the mixture was stirred for 3 h to finally obtain PDMHB-4.
[0035] Comparative Example 1:
[0036] 1.31 g of HMDI and 0.505 g of HDI were fully dissolved in 20 mL of THF, and then the solution was transferred to a three-necked round-bottom flask. 5.00 g of APT-PDMS and 1.20 g of D-400 were fully dissolved in 20 mL of THF, and then the solution was transferred to a constant-pressure funnel connected to the three-necked round-bottom flask. The mixed solution of APT-PDMS and D-400 was slowly added dropwise, and the mixture was stirred for 4 hours under a nitrogen atmosphere at a reaction temperature of 45 °C. Subsequently, the temperature was raised to 60 °C, and stirring was continued for 3 h without adding BIT, and finally PDMHB-0 was obtained.
Claims
1. Based on the related problems existing in the background technology, the polymer molecular chain structure can be adjusted, with aminopropyl dicapped polydimethylsiloxane (APT-PDMS, Mn = 1000g / mol) and polyetheramine (D-400) as soft segments, dicyclohexylmethane-4,4-diisocyanate (HMDI) and hexamethylene diisocyanate (HDI) as hard segments, and 2-aminobenzothiazole (BIT) introduced into the polymer main chain by chemical grafting to form a molecular network connected by all urea bonds, so as to comprehensively improve the mechanical properties and static antifouling ability of the material. A two-component silicone polyurea antifouling coating containing benzothiazole prepared by the present invention, The specific steps are as follows: (1) Dissolve 0.38-2.24 g of dicyclohexylmethane-4,4-diisocyanate (HMDI) and 0.323-1.023 g of hexamethylene diisocyanate (HDI) in 20 mL of tetrahydrofuran (THF), and then transfer the solution to a three-necked round-bottom flask. (2) 2.46-7.54 g of aminopropyl dicapped polydimethylsiloxane (APT-PDMS) and 0.48-1.92 g of polyetheramine (D-400) were fully dissolved in 20 mL of tetrahydrofuran (THF). (3) Then the solution in step 1 is transferred to a constant pressure funnel connected to a three-necked round-bottom flask, and slowly dripped into the mixed solution of aminopropyl di-terminated polydimethylsiloxane (APT-PDMS) and polyetheramine (D-400) in step (2), and stirred for 2 to 6 hours under a nitrogen atmosphere at a reaction temperature of 45°C. (4) The temperature was then raised to 60° C., 0.135 to 0.465 g of 2-aminobenzothiazole (BIT) was added to the precursor solution, and the mixture was stirred for 3 h.
2. According to the preferred embodiment of the present invention, in step (1), the amount of dicyclohexylmethane-4,4-diisocyanate (HMDI) used ranges from 0.38 to 2.24 g, preferably 1.31 g.
3. According to the preferred embodiment of the present invention, in step (1), the amount of hexamethylene diisocyanate (HDI) used ranges from 0.323 to 1.023 g, preferably 0.673 g.
4. Preferably according to the present invention, in step (2), the amount of aminopropyl di-terminated polydimethylsiloxane (APT-PDMS) used ranges from 2.46 to 7.54 g, preferably 5.00 g.
5. According to the preferred embodiment of the present invention, in step (2), the amount of polyetheramine (D-400) used ranges from 0.48 to 1.92 g, preferably 1.2 g.
6. According to the preferred embodiment of the present invention, in step (3), stirring is performed under a nitrogen atmosphere for 2 to 6 hours, preferably for 4 hours.
7. According to the preferred embodiment of the present invention, in step (4), the amount of 2-aminobenzothiazole (BIT) used ranges from 0.135 to 0.465 g, preferably 0.3 g.