Ecologically friendly marine antifouling coating with degradable, antibacterial and self-polishing properties and preparation method thereof

Abstract

The present application belongs to the field of synthesis of marine antifouling coatings, and particularly relates to an ecological friendly marine antifouling coating with degradability, antibiosis and self-polishing and a preparation method thereof. A multifunctional marine antifouling coating is prepared by catalyzing the reaction of elemental sulfur, binary or multi-acrylate and acrylate containing silicon groups by soluble organic base or cheap inorganic base with adjustable alkalinity. The binary or multi-acrylate enables the coating to have degradability, the introduction of elemental sulfur endows the coating with antibiosis, and the acrylate containing silicon groups provides the coating with excellent self-polishing effect. The synthesis method is efficient and simple, the catalysts and monomers that can be used are various, the polymerization conditions are mild, and the obtained marine antifouling coating integrates multiple functions, namely, degradability, antibiosis, self-polishing and good biocompatibility, thereby providing an effective way for the production of high-quality multifunctional marine antifouling coatings.

Description

Technical Field

[0001] This invention belongs to the field of marine antifouling coating synthesis, specifically relating to an eco-friendly marine antifouling coating with degradable, antibacterial and self-polishing properties and its preparation method. Background Technology

[0002] Expanding maritime space, developing marine resources, enriching marine industries, and safeguarding national maritime security all depend on marine equipment and facilities. However, the surfaces of marine equipment and facilities are inevitably subject to erosion by marine fouling organisms, causing serious economic costs and ecological environmental problems.

[0003] In recent years, with the increase in marine development activities, there has been a growing demand for eco-friendly antifouling methods. Existing self-polishing resins are mainly composed of vinyl polymers, and their antifouling effect relies on water flow, resulting in poor static antifouling performance and non-degradability, contributing to marine microplastic pollution. Furthermore, because they are linear polymers, functional modification is difficult, and the preparation of coatings requires large amounts of volatile organic compounds, further harming the environment. Therefore, the development of multifunctional marine antifouling systems by preparing high-solids-content, low-viscosity biodegradable polymers and endowing them with excellent antifouling properties and other functions through molecular design and structural optimization is of great practical significance. Summary of the Invention

[0004] This invention addresses the shortcomings of existing marine coatings by providing a multifunctional marine antifouling coating and its preparation method. The multifunctional marine antifouling coating is prepared by anionic hybrid copolymerization of elemental sulfur and binary or multi-component acrylates, as well as acrylates containing silicon groups, using a readily soluble, tunably alkaline organic base or an inexpensive inorganic base as catalysts.

[0005] The specific preparation process of the coating is as follows: Under normal pressure, elemental sulfur, binary or multi-component acrylates, acrylates containing silicon groups, and solvents are added to a flask, argon gas is introduced to replace the air in the flask, a catalyst is added, and polymerization is carried out at 25-150℃ for 3-24 hours. After cooling, the polymer is obtained.

[0006] Among them, the organic bases are triethylamine (TEA), tetramethylguanidine (TMG), 1,8-diazabicycloundec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,4-diazabicyclo[2.2.2]octane (DABCO), 4 - One or more of the following: dimethylaminopyridine (DMAP), tert-butylimino-tris(dimethylamino)phosphine (t-BuP1), 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2Λ5,4Λ5-di-bi(phosphine) (t-BuP2), and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphineimino]-2Λ5,4Λ5-di-bi(phosphine) (t-BuP4);

[0007] The inorganic base is one or more of sodium hydroxide (NaOH), potassium hydroxide (KOH), and calcium hydroxide (Ca(OH)2).

[0008] The solvent is one or more of toluene, xylene, tetrahydrofuran, 1,4-dioxane, and dichloromethane.

[0009] Di- or multi-component acrylates are one or more of the following: ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, (meth)acrylate-terminated polyethylene glycol (linear, branched), (meth)acrylate-terminated polycaprolactone (linear, branched), triethylene glycol di(meth)acrylate, and trihydroxy(meth)propane triacrylate.

[0010] The acrylates containing silicon groups are one or more of the following: triisopropylsilyl methacrylate, triisopropylsilyl acrylate, 3-(trimethoxysilane) methacrylate, 3-(trimethoxysilane) acrylate, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltriethoxysilane, and acrylate-terminated polysiloxanes (linear, branched).

[0011] The mass ratio of elemental sulfur to binary or polypropylene acrylates and acrylates containing silicon groups is (5-10):(10-40):(50-85).

[0012] The molar ratio of the catalyst to all monomers is 1:50 to 1000.

[0013] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0014] (1) The organic base catalyst used in the polymerization system has good solubility, adjustable alkalinity, requires a small amount, has a short reaction time, and is highly efficient. The inorganic base catalyst used is inexpensive and widely available.

[0015] (2) The polymer obtained in this invention has a structure of main chain degradation and side chain hydrolysis, which enables the coating to have both self-cleaning and self-polishing effects. At the same time, the introduction of elemental sulfur gives the coating an antibacterial effect. The degradation products are all small molecules with good biocompatibility, which will not cause secondary pollution to the ocean and are green and environmentally friendly.

[0016] (3) The polymerization method is novel, and the polymer functionalization is simple, the structure is controllable, and the performance is adjustable. Attached image description:

[0017] Figure 1 The image shows the 1H NMR spectrum of the polymerization product from Example 1.

[0018] Figure 2 The image shows the GPC curve of the product obtained in Example 1.

[0019] Figure 3 The image shows the DSC curve of the product obtained in Example 17.

[0020] Figure 4 The TG curve of the product obtained in Example 17.

[0021] Figure 5 The antibacterial properties of the product obtained in Example 17.

[0022] Figure 6 The degradation performance of the product obtained in Example 17 is shown.

[0023] Figure 7 The adhesion properties of the product obtained in Example 17.

[0024] Figure 8 The contact angle is the product obtained in Example 17. Detailed Implementation

[0025] 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.

[0026] Example 1

[0027] A magnetic rotor was added to a 250 mL flask, followed by 1,4-butanediol diacrylate (7.4 mL), triisopropylsilyl acrylate (20 mL), elemental sulfur (10 g), and tetrahydrofuran (100 mL). The mixture was stirred until homogeneous, and then DBU (0.7 mL) was added dropwise. Polymerization was carried out at 30 °C for 12 h, after which the reaction was complete.

[0028] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the vessel. The supernatant was discarded, and the product was dried in a vacuum oven to obtain a red solid with a yield of 89%. The polymer was characterized using nuclear magnetic resonance spectroscopy and gel permeation chromatography, and the results are as follows: Figure 1 and 2 As shown. The M of the obtained product w =13990 g / mol, molecular weight distribution is 2.11.

[0029] Example 2

[0030] A magnetic rotor was added to a 250 mL flask, followed by 7.4 mL of 1,4-butanediol diacrylate, 20 mL of triisopropylsilyl acrylate, 10 g of elemental sulfur, and 100 mL of xylene. The mixture was stirred until homogeneous, and then 0.7 mL of DBU was added dropwise. The reaction was terminated after polymerization at 30 °C for 12 h.

[0031] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the vessel. The supernatant was discarded, and the product was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 85%, and the molecular weight was M. w =10256 g / mol, molecular weight distribution is 2.07.

[0032] Example 3

[0033] A magnetic rotor was added to a 250 mL flask, followed by 1,4-butanediol diacrylate (7.4 mL), triisopropylsilyl acrylate (20 mL), elemental sulfur (10 g), and 1,4-dioxane (100 mL). The mixture was stirred until homogeneous, and then DBU (0.7 mL) was added dropwise. Polymerization was carried out at 30 °C for 12 h, after which the reaction was complete.

[0034] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 91%, and the molecular weight was M. w =15126 g / mol, molecular weight distribution is 1.98.

[0035] Example 4

[0036] A magnetic rotor was added to a 250 mL flask, followed by 7.4 mL of 1,4-butanediol diacrylate, 20 mL of triisopropylsilyl acrylate, 10 g of elemental sulfur, and 100 mL of xylene. The mixture was stirred until homogeneous, and then 0.7 mL of DBU was added dropwise. Polymerization was carried out at 100 °C for 6 h, after which the reaction was complete.

[0037] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 93%, and the molecular weight was M. w =14365 g / mol, molecular weight distribution is 1.86.

[0038] Example 5

[0039] A magnetic rotor was added to a 250 mL flask, followed by 1,4-butanediol diacrylate (10 mL), triisopropylsilyl acrylate (17 mL), elemental sulfur (12 g), and xylene (100 mL). The mixture was stirred until homogeneous, and then DBU (0.8 mL) was added dropwise. Polymerization was carried out at 30 °C for 12 h, after which the reaction was complete.

[0040] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the vessel. The supernatant was discarded, and the product was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 82%, and the molecular weight was M. w = 9865 g / mol, molecular weight distribution is 1.78.

[0041] Example 6

[0042] A magnetic rotor was added to a 250 mL flask, followed by 7.4 mL of 1,4-butanediol diacrylate, 20 mL of triisopropylsilyl acrylate, 10 g of elemental sulfur, and 100 mL of xylene. The mixture was stirred until homogeneous, and then 0.62 mL of DBN was added dropwise. The reaction was terminated after polymerization at 30 °C for 12 h.

[0043] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the vessel. The supernatant was discarded, and the product was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 90%, and the molecular weight was M. w = 8865 g / mol, molecular weight distribution is 1.94.

[0044] Example 7

[0045] A magnetic rotor was added to a 250 mL flask, followed by 7.4 mL of 1,4-butanediol diacrylate, 20 mL of triisopropylsilyl acrylate, 10 g of elemental sulfur, and 100 mL of xylene. The mixture was stirred until homogeneous, and then 0.56 g of TBD was added dropwise. The reaction was terminated after polymerization at 30 °C for 12 h.

[0046] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 95%, and the molecular weight was M. w=12563 g / mol, molecular weight distribution is 2.36.

[0047] Example 8

[0048] A magnetic rotor was added to a 250 mL flask, followed by 1,4-butanediol diacrylate (7.4 mL), triisopropylsilyl acrylate (20 mL), elemental sulfur (10 g), and xylene (100 mL). The mixture was stirred until homogeneous, and then t-BuP2 (0.02 mL) was added dropwise. The reaction was terminated after polymerization at 30 °C for 12 h.

[0049] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 92%, and the molecular weight was M. w =11569 g / mol, molecular weight distribution is 2.20.

[0050] Example 9

[0051] A magnetic rotor was added to a 250 mL flask, followed by 7.4 mL of 1,4-butanediol diacrylate, 20 mL of triisopropylsilyl acrylate, 10 g of elemental sulfur, and 100 mL of xylene. The mixture was stirred until homogeneous, and then 0.68 g of DABCO was added dropwise. The reaction was terminated after polymerization at 30 °C for 12 h.

[0052] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the vessel. The supernatant was discarded, and the product was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 84%, and the molecular weight was M. w =13620 g / mol, molecular weight distribution is 2.56.

[0053] Example 10

[0054] A magnetic rotor was added to a 250 mL flask, along with 7.4 mL of 1,4-butanediol diacrylate, 20 mL of triisopropylsilyl acrylate, 10 g of elemental sulfur, and 100 mL of xylene. The mixture was stirred until homogeneous, and then 1.32 g of NaOH was added dropwise. Polymerization was carried out at 60 °C for 12 h, after which the reaction was complete.

[0055] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 86%, and the molecular weight was M. w =11122 g / mol, molecular weight distribution is 1.95.

[0056] Example 11

[0057] A magnetic rotor was added to a 250 mL flask, followed by neopentyl glycol diacrylate (6.2 mL), triisopropylsilyl acrylate (20 mL), elemental sulfur (10 g), and xylene (100 mL). The mixture was stirred until homogeneous, and then DBU (0.7 mL) was added dropwise. The reaction was terminated after polymerization at 30 °C for 12 h.

[0058] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 80%, and the molecular weight was M. w =11420 g / mol, molecular weight distribution is 1.87.

[0059] Example 12

[0060] A magnetic rotor was added to a 250 mL flask, followed by acrylate-terminated polycaprolactone (21 g), triisopropylsilyl acrylate (20 mL), elemental sulfur (10 g), and xylene (100 mL). The mixture was stirred until homogeneous, and then DBU (0.7 mL) was added dropwise. Polymerization was carried out at 30 °C for 12 h, after which the reaction was complete.

[0061] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 92%, and the molecular weight was M. w =19962 g / mol, molecular weight distribution is 2.21.

[0062] Example 13

[0063] A magnetic rotor was added to a 250 mL flask, followed by 1,4-butanediol diacrylate (7.4 mL), 3-(trimethoxysilane)methacrylate (24 mL), elemental sulfur (10 g), and xylene (100 mL). The mixture was stirred until homogeneous, and then DBU (0.7 mL) was added dropwise. Polymerization was carried out at 30 °C for 12 h, after which the reaction was completed.

[0064] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 93%, and the molecular weight was M. w =11254 g / mol, molecular weight distribution is 1.89.

[0065] Example 14

[0066] A magnetic rotor was added to a 250 mL flask, along with 7.4 mL of 1,4-butanediol diacrylate, 35 mL of acrylate-terminated polysiloxane, 10 g of elemental sulfur, and 100 mL of xylene. The mixture was stirred until homogeneous, and then 0.7 mL of DBU was added dropwise. Polymerization was carried out at 30 °C for 12 h, after which the reaction was complete.

[0067] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the vessel. The supernatant was discarded, and the product was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 87%, and the molecular weight was M. w =23001 g / mol, molecular weight distribution is 2.36.

[0068] Example 15

[0069] A magnetic rotor was added to a 250 mL flask, followed by 10 mL of hydroxy(methyl)propane triacrylate, 20 mL of triisopropylsilyl acrylate, 10 g of elemental sulfur, and 100 mL of xylene. The mixture was stirred until homogeneous, and then 0.7 mL of DBU was added dropwise. The reaction was terminated after polymerization at 30 °C for 12 h.

[0070] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 94%, and the molecular weight was M. w = 9658 g / mol, molecular weight distribution is 2.36.

[0071] Example 16

[0072] A magnetic rotor was added to a 250 mL flask, along with 10 mL of hydroxy(methyl)propane triacrylate, 20 mL of triisopropylsilyl acrylate, 10 g of elemental sulfur, and 100 mL of xylene. The mixture was stirred until homogeneous, and then 5.2 mL of TEA was added dropwise. The reaction was terminated after polymerization at 30 °C for 12 h.

[0073] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 89%, and the molecular weight was M. w = 8321 g / mol, molecular weight distribution is 2.57.

[0074] Example 17

[0075] A magnetic rotor was added to a 250 mL flask, followed by 1,4-butanediol diacrylate (7.4 mL), triisopropylsilyl acrylate (18 mL), trimethylolpropane triacrylate (2 mL), elemental sulfur (11 g), and tetrahydrofuran (100 mL). The mixture was stirred until homogeneous, and then DBU (0.7 mL) was added dropwise. Polymerization was carried out at 30 °C for 12 h, after which the reaction was completed.

[0076] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the vessel. The supernatant was discarded, and the product was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 87%, and the molecular weight was M. w =12530 g / mol, molecular weight distribution is 2.27.

[0077] The product was characterized using differential scanning calorimetry and thermogravimetric analysis, and the results are as follows: Figure 3 and 4 As shown. Simultaneously, the product was tested for antibacterial and cytotoxic effects, and the results are as follows. Figure 5 As shown in Table 1.

[0078] Table 1

[0079]

[0080] Example 18

[0081] A magnetic rotor was added to a 250 mL flask, followed by 1,4-butanediol diacrylate (5 mL), triisopropylsilyl acrylate (10 mL), acrylate-terminated polysiloxane (22 mL), elemental sulfur (15 g), and tetrahydrofuran (100 mL). The mixture was stirred until homogeneous, and then DBU (0.7 mL) was added dropwise. Polymerization was carried out at 30 °C for 12 h, after which the reaction was complete.

[0082] Post-processing: After the reaction was stopped, the product precipitated in n-hexane, and the red filamentous solid settled at the bottom of the container. The supernatant was discarded, and the mixture was dried in a vacuum oven to obtain the red solid. The yield of the obtained product was 92%, and the molecular weight was M. w =12560g / mol, molecular weight distribution is 1.86.

Claims

1. An eco-friendly marine antifouling coating with biodegradable, antibacterial, and self-polishing properties, characterized in that: The marine antifouling coating is prepared by anionic hybrid copolymerization of elemental sulfur and binary or multi-component acrylates and acrylates containing silicon groups using organic or inorganic base catalysis. The mass ratio of elemental sulfur, binary or multi-component acrylates, and acrylates containing silicon groups is 5~10:10~40:50~85.

2. The eco-friendly marine antifouling coating with biodegradability, antibacterial properties, and self-polishing properties according to claim 1, characterized in that, The organic base is TEA, TMG, DMAP, DBU, TBD, DBN, MTBD, or DABCO. t- BuP1、 t- BuP2、 t- One or more of BuP4.

3. The eco-friendly marine antifouling coating with biodegradability, antibacterial properties, and self-polishing properties according to claim 1, characterized in that, The inorganic base is one or more of NaOH, KOH, and Ca(OH)2.

4. The eco-friendly marine antifouling coating with biodegradability, antibacterial properties, and self-polishing properties according to claim 1, characterized in that, The binary or multi-component acrylates are: ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, linear (meth)acrylate-terminated polyethylene glycol or branched (meth)acrylate-terminated polyethylene glycol, linear (meth)acrylate-terminated polycaprolactone or branched (meth)acrylate-terminated polycaprolactone, triethylene glycol di(meth)acrylate, and trihydroxy(meth)propane triacrylate.

5. The eco-friendly marine antifouling coating with biodegradability, antibacterial properties, and self-polishing properties according to claim 1, characterized in that, The acrylate containing silicon groups is: triisopropylsilyl methacrylate, triisopropylsilyl acrylate, 3-(trimethoxysilane) methacrylate, 3-(trimethoxysilane) acrylate, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltriethoxysilane, linear acrylate-terminated polysiloxane, or branched acrylate-terminated polysiloxane.

6. A method for preparing an eco-friendly marine antifouling coating with biodegradability, antibacterial properties, and self-polishing properties according to claim 1, characterized in that, The preparation method is as follows: under normal pressure, elemental sulfur, binary or multi-component acrylates, acrylates containing silicon groups and solvents are added to a flask, the air in the flask is replaced by argon gas, and a catalyst is added to carry out a polymerization reaction.

7. The method for preparing the eco-friendly marine antifouling coating with biodegradability, antibacterial properties, and self-polishing as described in claim 6, characterized in that, The molar ratio of the catalyst to all monomers is 1:50~1000, the reaction temperature is 25~150℃, and the reaction time is 3~24 h.

8. The method for preparing the eco-friendly marine antifouling coating with biodegradability, antibacterial properties, and self-polishing as described in claim 6, characterized in that, The solvent is one or more of toluene, xylene, tetrahydrofuran, 1,4-dioxane, ethyl acetate, and dichloromethane.

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