Preparation method of low surface energy type hydrophobic marine antifouling paint

[0021] Example 1

[0022] Weigh 16g of nanometer titanium dioxide and 12g of nanometer silicon dioxide, grind and grind for 8 minutes, pass through a 100-mesh sieve, collect the sieved powder, according to the mass ratio of 3:5:1:1, the sieved powder, distilled water, sesame oil and silane coupling agent KH-570 was mixed and placed in a 500mL flask and stirred for 6 minutes, and then the stirred flask was placed in an ultrasonic disperser for ultrasonic dispersion for 16 minutes. After dispersion, it was heated and refluxed at 80°C for 2 hours to obtain a reaction solution. After washing the reaction solution for 4 minutes, it is air-dried naturally, and the material is grinded to obtain a modified sieved powder. Measure 45mL xylene, 12mL methyl methacrylate, 6mL butyl acrylate and 1mL acrylic acid, mix and pour it into containing 2g azobisisobutyl Shake the nitrile constant pressure dropping funnel for 6 minutes to obtain a self-made mixture. Then add 35 mL of xylene to a four-necked flask equipped with a condenser, agitator and a thermometer, and stir for 4 minutes at a temperature of 60°C. Add the homemade mixed solution dropwise to the flask, keep stirring and react for 1 hour, continue to add 1g of azobisisobutyronitrile to the four-necked flask, mix and react for 1 hour, cool to room temperature naturally, and discharge the homemade acrylic resin. After mixing and grinding with crab shells for 6 minutes, a mixed shell powder is obtained. The mixed shell powder and 5% by mass hydrochloric acid are soaked in a beaker with a mass ratio of 1:3 for 1 hour to remove calcium carbonate in the shell to obtain a mixed shell after soaking Powder, put the soaked mixed shell powder into a 10% sodium hydroxide solution twice the mass of the soaked mixed shell powder and boil for 1 hour to remove the protein in the shell, and continue to pour the soaked mixed shell powder mass 1 times the mass fraction of 35% sodium hydroxide solution, hydrolyzed at a temperature of 100 ℃ for 2 hours, after hydrolysis, put it in an oven at 80 ℃ for 2 hours, after drying, you can get homemade chitosan, according to the mass ratio of 1 :2 Mix and dissolve the homemade chitosan and 3% acetic acid solution for 1 hour to obtain the homemade chitosan solution. In parts by weight, weigh 24 parts of homemade acrylic resin and 16 parts of modified sieving. Mix the powder, 10 parts of homemade chitosan solution, 6 parts of rosin and 8 parts of deionized water in a blender, stir at 45℃ for 16 minutes, then add 3 parts of chlorinated paraffin, 1 part of cuprous oxide and 2 parts For xylene, continue mixing and stirring at a temperature of 65°C for 1 hour, cooling to room temperature naturally, and discharging to obtain a low surface energy hydrophobic marine antifouling paint.

[0023] Example 2

[0024] Weigh 18g of nanometer titanium dioxide and 14g of nanometer silicon dioxide, mix, grind and grind for 9 minutes, pass through a 100-mesh sieve, collect the sieved powder, according to the mass ratio of 3:5:1:1, sieve the powder, distilled water, sesame oil and silane coupling agent KH-570 was mixed and placed in a 500mL flask and stirred for 7 minutes, and then the stirred flask was placed in an ultrasonic disperser for ultrasonic dispersion for 18 minutes. After dispersion, it was heated and refluxed for 3 hours at a temperature of 90℃ to obtain a reaction solution. After washing the reaction solution for 5 minutes, it is air-dried naturally, and the material is grinded to obtain a modified sieved powder. Measure 50mL xylene, 14mL methyl methacrylate, 7mL butyl acrylate and 2mL acrylic acid, mix and pour into the mixture containing 3g azobisisobutyl Shake the nitrile constant pressure dropping funnel for 7 minutes to obtain a self-made mixture. Then add 45 mL of xylene to a four-necked flask equipped with a condenser, agitator and a thermometer, and stir for 5 minutes at a temperature of 70°C. Add the homemade mixed solution dropwise to the flask, keep stirring and react for 1.5h, continue to add 2g of azobisisobutyronitrile to the four-necked flask, mix and react for 1.5h, cool to room temperature naturally, and discharge the homemade acrylic resin. Shrimp shells and crab shells were mixed and ground for 7 minutes to obtain mixed shell powder. The mixed shell powder and 5% hydrochloric acid were soaked in a beaker with a mass ratio of 1:3 for 1.5 hours to remove the calcium carbonate in the shell. Put the soaked mixed shell powder into a 10% sodium hydroxide solution with a mass fraction of 3 times the mass of the soaked mixed shell powder and boil for 1.5h to remove the protein in the shell and continue to pour the soaked mixed shell powder Mix the shell powder in a 35% sodium hydroxide solution with a mass fraction of 2 times the mass, hydrolyze it at 110°C for 3 hours, and place it in an oven at 90°C for 3 hours after hydrolysis. After drying, homemade chitosan is obtained. According to the mass ratio of 1:2, the homemade chitosan and the 3% acetic acid solution were mixed, stirred and dissolved for 1.5h to obtain the homemade chitosan solution. In parts by weight, weigh 28 parts of homemade acrylic resin and 18 parts respectively. Mix 1 parts modified sieved powder, 11 parts homemade chitosan solution, 7 parts rosin and 9 parts deionized water in a mixer, stir at 50℃ for 18 minutes, then add 4 parts chlorinated paraffin and 2 parts oxidation Cuprous and 3 parts of xylene, continue to mix and stir for 2h at a temperature of 75°C, cool to room temperature naturally, and discharge the material to obtain a low surface energy hydrophobic marine antifouling paint.

[0025] Example 3

[0026] Weigh 20g of nano-titanium dioxide and 16g of nano-silica, mix, grind and grind for 10 minutes, pass through a 100-mesh sieve, collect the sieved powder, and mix the sieved powder, distilled water, sesame oil and silane coupling agent at a mass ratio of 3:5:1:1 KH-570 was mixed and placed in a 500mL flask and stirred for 8 minutes, then the stirred flask was placed in an ultrasonic disperser for ultrasonic dispersion for 20 minutes. After dispersion, it was heated and refluxed for 4 hours at a temperature of 100°C to obtain a reaction solution. After washing the reaction solution for 6 minutes, it is naturally air-dried and the material is grinded to obtain a modified sieved powder. Measure 55 mL of xylene, 16 mL of methyl methacrylate, 8 mL of butyl acrylate and 3 mL of acrylic acid, mix and pour into the mixture containing 4 g of azobisisobutyl Shake the nitrile constant pressure dropping funnel for 8 minutes to obtain a self-made mixture. Then add 55 mL of xylene into a four-necked flask equipped with a condenser, a stirrer and a thermometer, and stir for 6 minutes at a temperature of 80°C. Add the homemade mixed solution dropwise to the flask, keep stirring and react for 2h, continue to add 3g azobisisobutyronitrile to the four-necked flask, mix and react for 2h, cool to room temperature naturally, discharge the homemade acrylic resin, and divide the shrimp shells with equal mass ratio After mixing and grinding with crab shells for 8 minutes, the mixed shell powder is obtained. The mixed shell powder and 5% hydrochloric acid are soaked in a beaker with a mass ratio of 1:3 for 2 hours to remove the calcium carbonate in the shell to obtain the soaked mixed shell. Powder, put the soaked mixed shell powder into a 10% sodium hydroxide solution with 4 times the mass of the soaked mixed shell powder and boil for 2h to remove the protein in the shell, and continue to pour into the soaked mixed shell powder mass 3 times the mass fraction of 35% sodium hydroxide solution, hydrolyzed at a temperature of 120 ℃ for 4 hours, hydrolyzed in an oven at 100 ℃ for 4 hours, after drying, the homemade chitosan can be obtained, according to the mass ratio of 1 :2 Mix and dissolve the homemade chitosan and 3% acetic acid solution for 2h to obtain the homemade chitosan solution. In parts by weight, weigh 32 parts of homemade acrylic resin and 20 parts of modified sieving Mix the powder, 12 parts of homemade chitosan solution, 8 parts of rosin and 10 parts of deionized water in a blender, stir for 20 minutes at a temperature of 55℃, and then add 5 parts of chlorinated paraffin, 3 parts of cuprous oxide and 4 parts For xylene, continue to mix and stir for 3 hours at a temperature of 85°C, cool to room temperature naturally, and discharge the material to obtain a low surface energy hydrophobic marine antifouling paint.