Antifouling biological adhesive agent and antifouling biological adhesive coating

[0052] Example 1

[0053] Step1. Preparation of polyaspartate, code name PAE-a

[0054] The amino-terminated polyether Jeffamine D-2000 and diethyl maleate are compared to n(-NH 2 ): n(-C=C-)=1:1 measurement. Add Jeffamine D-2000 into a reactor equipped with a stirrer and a heating and temperature control device, ventilate nitrogen and increase the temperature to 40°C, add diethyl maleate dropwise at a rate of one drop every two seconds. After the addition is complete, nitrogen protection Under stirring, heat to 80°C, keep for 24h, and cool down to produce polyaspartate.

[0055] Step2. Preparation of A component of polyaspartate coating

[0056] The amount of 2,4'-diphenylmethane diisocyanate MDI-50 and polyoxypropylene glycol PPG2000 is measured according to the NCO% of the resulting prepolymer = 15%. Add 2,4'-diphenylmethane diisocyanate MDI-50 into a reactor equipped with a stirrer and a heating and temperature control device, ventilate nitrogen and heat up to 40°C, add polyoxypropylene glycol PPG2000 dropwise at a rate of One drop in two seconds. After the addition is complete, stir and heat to 75°C under nitrogen protection, and continuously measure the NCO content. When the NCO mass percentage changes ≤0.05%, stop the reaction, cool down and stir evenly to discharge the isocyanate prepolymer, which is used as paint A Components.

[0057] Step3. Preparation of surface modified shell powder

[0058] The shell powder obtained by recycling the waste shells, alkaline washing for 24 hours, clean water washing, drying and grinding, has an average particle diameter of 0.1 μm-100 μm. Weigh an appropriate amount of shell powder after grinding, add it to the water at a solid-liquid ratio of 1:10, and heat up to 90°C for 30 minutes to obtain shell slurry; the added amount of surface modifier sodium stearate is the quality of the shell powder 1%, after adding it to a small amount of hot water to dissolve it, adding it to a constant temperature shell slurry and reacting for 30 minutes, suction filtration, drying and grinding to obtain modified shell powder.

[0059] Step4. Preparation of anti-fouling biological adhesion agent

[0060] (1) Preparation of styrene and acrylic acid copolymer microsphere template

[0061] In a 250 mL three-necked flask, 100 mL of absolute ethanol, 1.25 g of polyvinylpyrrolidone, 0.5 mL of acrylic acid, and 28 mL of styrene dissolved with 0.30 g of azobisisobutyronitrile were sequentially added, and stirred to form a homogeneous system. Advance access N 2 After deoxygenation for 30 minutes, the temperature was quickly raised to 70°C, and the reaction was kept constant for 24 hours. Centrifuge the polymerized emulsion and discard the supernatant. After washing with ethanol for several times, it is naturally dried at room temperature, and then placed in an infrared lamp to be thoroughly dried to obtain white styrene and acrylic acid copolymer microsphere powder.

[0062] (2) Preparation of white styrene and acrylic acid copolymerized microspheres/silica core-shell microspheres

[0063] Weigh 0.4 g of white styrene and acrylic acid copolymer microsphere template, and ultrasonically disperse with 20 mL of absolute ethanol. Add 0.4 mL of water and 0.4 mL of ammonia to the dispersion and stir for 5 min, then add 0.6 mL of tetraethyl orthosilicate, seal the bottle with plastic wrap, and react at 30° C. for 8 hours. Centrifugation, washing, and drying to obtain styrene and acrylic acid copolymer microspheres/silica core-shell microspheres.

[0064] (3) Preparation of zinc oxide/silica hollow microspheres

[0065] Weigh 3mmol of zinc nitrate hexahydrate and 4.5g of styrene and acrylic acid copolymerized microspheres/silica core-shell microspheres in a 250mL round-bottomed flask, add 200mL of distilled water, stir well, add 0.5mmol of sodium citrate, and stir well Add 30 mL of ammonia water, and white precipitates are generated in the solution and disappear immediately. The flask is placed in an oil bath and heated to 120°C with stirring and refluxing. The obtained white precipitate is centrifuged, and fully washed with deionized water, and dried in air to obtain zinc oxide/styrene and acrylic acid copolymerized microspheres/silica core-shell microspheres. Finally, the zinc oxide/styrene and acrylic acid copolymerized microspheres/silica core-shell microspheres are placed in a crucible, and the temperature is slowly raised to 400°C in an air atmosphere, and the temperature is kept for 5 hours, and the heating rate is 1°C/min.

[0066] (4) Surface modified zinc oxide/silica hollow microspheres with organosilicon quaternary ammonium salt antibacterial agent

[0067] Weigh an appropriate amount of 5g of zinc oxide/silica hollow microspheres and 1g of organosilicon quaternary ammonium salt and dissolve them in 100mL of deionized water, mix and stir for 3h at room temperature at low speed, and then add 1mol/L oxalic acid dropwise to adjust the mixing Solution pH to 3. After standing for 24 hours, ultrasonic washing was repeated, drying at 110°C, and grinding.

[0068] (5) Preparation of imidazoline quaternary ammonium salt

[0069] Add a small amount of ceramic particles and 0.13mol of tetraethylenepentamine into a three-necked flask connected with a thermometer, a spherical condenser, and a stirrer. The temperature is increased to 110°C and 6.5g of calcium oxide is added as a dewatering agent, and added dropwise with a constant pressure separatory funnel. 0.1mol lauric acid ester, drip in 30 minutes, heat up to 150-160℃, carry out intermolecular amidation and dealcoholization reaction for 5h; continue to stir and heat up to 210-220℃, carry out intramolecular cyclization dehydration reaction for 5h, and get imidazole The above-mentioned imidazoline intermediate is cooled to 90-100°C, and sodium chloroacetate is added dropwise according to the molar ratio of the imidazoline intermediate to sodium chloroacetate at a ratio of 1:1.1, and the quaternization reaction is carried out with constant temperature stirring for 5h, Prepare imidazoline quaternary ammonium salt.

[0070] (6) Preparation of modified zinc dioxide/silica hollow microspheres loaded with antibacterial agents

[0071] Weigh 0.5g of modified zinc oxide/silica hollow microspheres, add 40mL of imidazoline quaternary ammonium salt with a concentration of 40mg/mL in a three-necked flask, vacuum pump for 15min, remove the flask and zinc oxide/dioxide The air in the hollow silicon microspheres. Open the funnel piston and turn on the ultrasonic device at the same time. After the liquid is completely immersed in the zinc oxide/silica microspheres and the ultrasonic dispersion is uniform, withdraw from the decompression device and stir at room temperature for 8 hours. During this stirring period, ultrasonic for 1 min every 2 h. After centrifugation, the supernatant was discarded, and the hollow microspheres were vacuum dried at 60° C. for 24 hours to obtain the anti-fouling biological adhesion agent. Such as figure 1 As shown, the anti-fouling biological adhesion agent is a surface-modified silicone quaternary ammonium salt 3 containing imidazoline quaternary ammonium salt 4 zinc oxide 2 / silica 1 hollow microspheres, wherein the imidazoline The quaternary ammonium salt 4 is loaded in the hollow core of the hollow microspheres of zinc oxide 2 / silica 1, and the organosilicon quaternary ammonium salt 3 is on the surface of the hollow microspheres of zinc oxide 2 / silica 1.

[0072] Step5. Preparation of B component of polyaspartate coating

[0073] Weigh 65 parts of polyaspartic acid ester PAE-a of Step1, 10 parts of shell powder, 10 parts of titanium dioxide, 8 parts of talc, 5 parts of anti-biological adhesion agent, 2 parts of additives, and then add them to the cylinder at high speed. Stir for 1h, mix and discharge evenly, as the coating B component.

[0074] When in use, the molar ratio of -NCO in component A to -NH in component B is 1.05-1.1:1 for mixing.

[0075] Example 2

[0076] Step1. Preparation of polyaspartate, code name PAE-b

[0077] The amino-terminated polyether Jeffamine T-5000 and diethyl maleate are compared by the amount of substance n(-NH 2 ): n(-C=C-)=1:1 measurement. Add Jeffamine T-5000 into a reactor equipped with a stirrer and heating and temperature control device, ventilate nitrogen and heat to 40°C, add diethyl maleate dropwise at a rate of one drop every two seconds. After the addition is complete, nitrogen protection Under stirring, heat to 80°C, keep for 24h, and cool down to produce polyaspartate.

[0078] Step2. Preparation of A component of polyaspartate coating

[0079] The amount of 2,4'-diphenylmethane diisocyanate MDI-50 and polyoxypropylene glycol PPG2000 is measured according to the NCO% of the resulting prepolymer = 15%. Add 2,4'-diphenylmethane diisocyanate MDI-50 into a reactor equipped with a stirrer and a heating and temperature control device, blow nitrogen and heat up to 40℃, add polyoxypropylene glycol PPG2000 dropwise, blow nitrogen and heat up When the temperature reaches 40℃, add polyoxypropylene glycol PPG2000 dropwise at a rate of one drop every two seconds. After the addition is complete, stir and heat to 75℃ under nitrogen protection, and continuously measure the NCO content. When the NCO mass percentage change is ≤0.05% The reaction is stopped, the temperature is lowered and stirred evenly, and the material is discharged as an isocyanate prepolymer as the A component of the coating.

[0080] Step3. Preparation of surface modified shell powder

[0081] The shell powder obtained by recycling and washing the waste shells, alkaline washing for 18 hours, clean water washing, drying and grinding, has an average particle size of 0.1 μm-100 μm. Weigh an appropriate amount of ground shell powder, add it to water at a solid-liquid ratio of 1:10, and raise the temperature to 80°C for 30 minutes. The addition amount of the surface modifier aluminate coupling agent is 1.5% of the mass of the shell powder. After adding a small amount of toluene to dissolve it, adding it to the shell slurry at a constant temperature and reacting for 30 minutes, suction filtration, vacuum drying, and grinding to obtain Modified shell powder.

[0082] Step4. Preparation of anti-fouling biological adhesion agent

[0083] (1) Preparation of styrene and acrylic acid copolymer microsphere template

[0084] The experimental conditions are the same as in Example 1.

[0085] (2) Preparation of white styrene and acrylic acid copolymerized microspheres/silica core-shell microspheres

[0086] Weigh 0.4 g of white styrene and acrylic acid copolymerized microsphere template, and ultrasonically disperse with 50 mL of absolute ethanol. Add 1 mL of water and 0.75 mL of ammonia to the dispersion and stir for 10 min, then add 0.6 mL of tetraethyl orthosilicate, seal the bottle with plastic wrap, and react at 25° C. for 12 hours. Centrifugation, washing, and drying to obtain styrene and acrylic acid copolymer microspheres/silica core-shell microspheres.

[0087] (3) Preparation of zinc oxide/silica hollow microspheres

[0088] Weigh 3mmol of zinc nitrate hexahydrate and 4.5g of styrene and acrylic acid copolymerized microspheres/silica core-shell microspheres into a 250mL round bottom flask, add 200mL of distilled water, stir well, add 1mmol of sodium citrate, stir well and then add Ammonia water 30mL, a white precipitate appeared in the solution and disappeared immediately, the flask was placed in an oil bath and heated to 160°C and refluxed for 12 hours. The obtained white precipitate is centrifuged, and fully washed with deionized water, and dried in air to obtain zinc oxide/styrene and acrylic acid copolymerized microspheres/silica core-shell microspheres. Finally, the zinc oxide/styrene and acrylic acid copolymerized microspheres/silica core-shell microspheres were placed in a crucible, and the temperature was slowly raised to 500°C in an air atmosphere, and the temperature was kept for 5 hours, and the temperature rising rate was 1°C/min.

[0089] (4) Surface modified zinc oxide/silica hollow microspheres with organosilicon quaternary ammonium salt antibacterial agent

[0090] Weigh an appropriate amount of 5g zinc oxide/silica hollow microspheres and 2g organosilicon quaternary ammonium salt and dissolve them in 100mL deionized water, mix and stir at room temperature at low speed for 3h, and then add 0.5mol/L oxalic acid dropwise under stirring. The pH of the mixed solution is 3. After standing for 24 hours, ultrasonic washing was repeated, dried at 100°C, and ground.

[0091] (5) Preparation of imidazoline quaternary ammonium salt

[0092] Add a small amount of ceramic particles and 0.18 mol of diethylene triamine into a three-necked flask connected with a thermometer, a spherical condenser, and a stirrer. The temperature is increased to 110°C and 6.5 g of calcium oxide is added as a dewatering agent, and added dropwise with a constant pressure separatory funnel. 0.15 mol of methyl oleate, drip in 30 minutes, heat up to 140-150°C, carry out intermolecular amidation and dealcoholization reaction for 3.5h; continue to stir and heat up to 200-210°C, carry out intramolecular cyclization dehydration reaction for 3 hours, and get Imidazoline intermediate; cool the above-mentioned imidazoline intermediate to 90-100℃, add benzyl chloride dropwise according to the molar ratio of imidazoline intermediate to benzyl chloride of 1:1.1, constant temperature, stirring quaternization reaction 3.5 h, prepare imidazoline quaternary ammonium salt.

[0093] (6) Preparation of modified zinc dioxide/silica hollow microspheres loaded with antibacterial agents

[0094] Weigh 0.5g of modified zinc oxide/silica hollow microspheres, add 40mL of 50mg/mL imidazoline quaternary ammonium salt in a three-necked flask, vacuum pump for 15min, remove the flask and zinc oxide/dioxide The air in the hollow silicon microspheres. Open the funnel piston and turn on the ultrasonic device at the same time. After the liquid is completely immersed in the zinc oxide/silica microspheres and the ultrasonic dispersion is uniform, withdraw from the decompression device and stir at room temperature for 10 hours. During this stirring period, ultrasonic 2min every 2h. After centrifugation, the supernatant was discarded, and the hollow microspheres were vacuum dried at 60° C. for 24 hours to obtain the anti-fouling biological adhesion agent.

[0095] Step5. Preparation of B component of polyaspartate coating

[0096] Weigh 60 parts of polyaspartate PAE-b of Step1, 8 parts of shell powder, 8 parts of quartz sand, 8 parts of titanium dioxide, 5 parts of talc, 8 parts of anti-biological adhesion agent, 3 parts of additives, and add them in sequence In the cylinder, stir at high speed for 1 hour, mix and discharge evenly, as the coating B component.

[0097] When in use, the molar ratio of -NCO in component A to -NH in component B is 1.05-1.1:1 for mixing.

[0098] Example 3

[0099] Step1. Preparation of polyaspartate, code name PAE-c

[0100] The amino-terminated polyether Jeffamine T-403 and diethyl maleate are compared to n(-NH 2 ): n(-C=C-)=1:1 measurement. Add Jeffamine T-403 into a reactor equipped with a stirrer and a heating and temperature control device, ventilate nitrogen and heat to 40°C, add diethyl maleate dropwise at a rate of one drop every two seconds. After the addition is complete, nitrogen protection Under stirring, heat to 80°C, keep for 24h, and cool down to produce polyaspartate.

[0101] Step2. Preparation of A component of polyaspartate coating

[0102] The amount of 2,4'-diphenylmethane diisocyanate MDI-50 and polyoxypropylene glycol PPG2000 is measured according to the NCO% of the resulting prepolymer = 15%. Add 2,4'-diphenylmethane diisocyanate MDI-50 into a reactor equipped with a stirrer and a heating and temperature control device, blow nitrogen and heat up to 40℃, add polyoxypropylene glycol PPG2000 dropwise, blow nitrogen and heat up When the temperature reaches 40℃, add polyoxypropylene glycol PPG2000 dropwise at a rate of one drop every two seconds. After the addition is complete, stir and heat to 75℃ under nitrogen protection, and continuously measure the NCO content. When the NCO mass percentage change is ≤0.05% The reaction is stopped, the temperature is lowered and stirred evenly, and the material is discharged as an isocyanate prepolymer as the A component of the coating.

[0103] Step3. Preparation of surface modified shell powder

[0104] The shell powder obtained by recycling and washing the waste shells, alkaline washing for 12 hours, washing with clear water, drying and grinding, has an average particle size of 0.1 μm-100 μm. Weigh an appropriate amount of ground shell powder and put it into a high-speed mixer at a speed of 1500 rpm. The surface modifier aluminate coupling agent was sprayed into a high-speed mixer with shell powder and stirred for 15 minutes. Then, the shell powder is compound modified by adding modifier sodium stearate by spraying, stirring time is 10 minutes, discharging and drying, and the product is obtained.

[0105] Step4. Preparation of anti-fouling biological adhesion agent

[0106] (1) Preparation of cetyltrimethylammonium bromide/silica core-shell microspheres

[0107] Add 15mL ethanol, 25 water, 0.5 ammonia water and 0.08g cetyltrimethylammonium bromide to a 250mL three-necked flask, stir and dissolve at 25, then add 0.5 tetraethyl orthosilicate, react for 3h to stop the reaction, wash and filter , Dry the sample at 120°C.

[0108] (2) Preparation of zinc oxide/silica hollow microspheres

[0109] Weigh 5mmol zinc nitrate hexahydrate and 4.5g cetyltrimethylammonium bromide/silica core-shell microspheres into a 250mL round bottom flask, add 200mL distilled water, stir well, add 0.5mmol sodium citrate, After fully stirring, add 50 mL of ammonia water, and white precipitation will appear in the solution and disappear immediately. The flask is heated to 150°C and refluxed for 12 hours in an oil bath. Centrifugal separation of the obtained white precipitate, fully wash with deionized water, and dry in the air to obtain zinc oxide/hexadecyltrimethylammonium bromide/silica core-shell microspheres. Finally, the zinc oxide/hexadecyltrimethylammonium bromide/silica core-shell microspheres are placed in a crucible, and in an air atmosphere, the temperature is slowly raised to 400℃, and the temperature is kept for 5h, the heating rate is 1℃/min .

[0110] (4) Surface modified zinc oxide/silica hollow microspheres with organosilicon quaternary ammonium salt antibacterial agent

[0111] Weigh an appropriate amount of 5g zinc oxide/silica hollow microspheres and 1.5g organosilicon quaternary ammonium salt and dissolve them in 100mL deionized water, mix and stir at room temperature at low speed for 3h, and then add 0.3mol/L oxalic acid dropwise under stirring Adjust the pH of the mixed solution to 3. After standing for 24 hours, ultrasonic washing was repeated, drying at 110°C, and grinding.

[0112] (5) Preparation of modified zinc dioxide/silica hollow microspheres loaded with antibacterial agents

[0113] Weigh 1.25g of modified zinc oxide/silica hollow microspheres and add them to a three-necked flask containing 50mL of potassium sorbate with a concentration of 50mg/mL. Pump under reduced pressure for 15 minutes to remove the flask and zinc oxide/silica hollows The air in the microspheres. Open the funnel piston and turn on the ultrasonic device at the same time. After the liquid is completely immersed in the zinc oxide/silica microspheres and the ultrasonic dispersion is uniform, withdraw from the decompression device and stir at room temperature for 8 hours. During this stirring period, ultrasonic for 1 min every 2 h. After centrifugation, the supernatant was discarded, and the hollow microspheres were vacuum dried at 60° C. for 24 hours to obtain the anti-fouling biological adhesion agent.

[0114] Step5. Preparation of B component of polyaspartate coating

[0115] Weigh 55 parts of polyaspartate PAE-c of Step1, 8 parts of shell powder, 7 parts of quartz sand, 7 parts of talc, 10 parts of titanium dioxide, 10 parts of anti-biological adhesion agent, 3 parts of additives, and then add them to In the cylinder, stir at high speed for 1 hour, mix and discharge the material evenly, as the coating B component.

[0116] When in use, the molar ratio of -NCO in component A to -NH in component B is 1.05-1.1:1 for mixing.