Anti-aging flame-retardant black disperse dye and preparation method thereof

Abstract

The present invention discloses an anti-aging flame-retardant black disperse dye and a preparation method thereof, relating to the field of nano-carbon black. In the preparation of the anti-aging flame-retardant black disperse dye, the present invention comprises the following steps: oxidizing nano-carbon black with nitric acid and reacting it with silver nitrate to obtain silver-loaded nano-carbon black; polymerizing ethyl orthosilicate and 3-chloropropyltrimethoxysilane on the surface of the silver-loaded nano-carbon black to obtain transparent silicon-coated carbon black; reacting the transparent silicon-coated carbon black with ethyl hypophosphite to obtain modified transparent silicon-coated carbon black; and then reacting the modified transparent silicon-coated carbon black with 3,4-epoxy-1-butene and methyl 5-allyl-3-methoxysalicylate to obtain the anti-aging flame-retardant black disperse dye. The anti-aging flame-retardant black disperse dye prepared by the present invention has excellent antibacterial properties, aging resistance, flame retardancy, and wear resistance.

Description

Technical Field

[0001] The invention relates to the field of nano carbon black, in particular to an anti-aging flame-retardant black disperse dye and a preparation method thereof. Background Art

[0002] Black is a key hue in reactive dye color systems. High-quality black dyes require high concentrations and require deep color, high blackness, and excellent fastness, making their preparation challenging. To produce high-concentration, stable black reactive dyes, multiple reactive dyes of different colors are typically combined to create a darker, more stable black color. However, combining multiple dyes creates a complex black reactive dye system, as interactions between dyes, solvents, and water molecules can affect stability and color purity.

[0003] Traditional benzidine-type azo dyes have the advantages of good blackness, high dye uptake and fixation rate, but they release carcinogens during use, which limits their use. Nano carbon black is widely used in black inks and coatings due to its excellent blackness, weather resistance, chemical stability, low price, and wide availability. It is the main colorant for black in paint dyeing. Carbon black has a large specific surface area and surface energy, and a strong cohesive force, which makes carbon black particles very easy to aggregate. However, since carbon black has fewer hydrophilic groups on its surface and has a certain hydrophobicity, it is difficult to form an effective bond with other components in inorganic or other organic solvents, which limits the application of the excellent performance of carbon black. Therefore, the present invention prepares an anti-aging flame-retardant black disperse dye with excellent binding effect. Summary of the Invention

[0004] The object of the present invention is to provide an anti-aging flame-retardant black disperse dye and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] The invention discloses an anti-aging flame-retardant black disperse dye, which is obtained by reacting modified transparent silicon-encapsulated carbon black, 3,4-epoxy-1-butene and 5-allyl-3-methoxy methyl salicylate.

[0007] As an optimization, the modified transparent silicon-coated carbon black is obtained by reacting transparent silicon-coated carbon black and ethyl hypophosphite.

[0008] As an optimization, the transparent silicon-wrapped carbon black is obtained by polymerizing ethyl orthosilicate and 3-chloropropyltrimethoxysilane on the surface of silver-loaded nano-carbon black.

[0009] As an optimization, the silver-loaded nano-carbon black is obtained by reacting nano-carbon black with silver nitrate after being oxidized by nitric acid.

[0010] As an optimization, the nano carbon black model is N330, which comes from Dongguan Dingxin Plastic Raw Materials Co., Ltd.

[0011] A method for preparing an anti-aging flame-retardant black disperse dye comprises the following preparation steps:

[0012] (1) Nano carbon black and nitric acid solution with a mass fraction of 67% to 69% are mixed in a mass ratio of 1:(9-11), ultrasonically dispersed for 25-35 minutes, stirred and refluxed at 75-85°C and 100-200 rpm for 2-4 hours, naturally cooled to room temperature and then the upper acid solution is poured out, washed with deionized water for 3-5 times, and dried at 105-115°C for 3-5 hours to obtain oxidized carbon black; oxidized carbon black and deionized water are mixed in a mass ratio of 1:(1 99-201) and uniformly mixed, ultrasonically dispersed at 20-30° C. for 10-20 min, added with 0.1-0.3 mol / L silver nitrate solution (150-250 times the mass of oxidized carbon black), adjusted the solution pH to 6-7, stirred at 60-70° C. and 200-300 rpm for 5-6 h, naturally cooled to room temperature, filtered, washed with deionized water 3-5 times, and dried at 115-125° C. for 3-5 h to obtain silver-loaded nanocarbon black;

[0013] (2) Ethyl orthosilicate, 3-chloropropyltrimethoxysilane and anhydrous ethanol are mixed in a mass ratio of 1: (0.9-1.1): (7-9) to obtain a silicon source mixed solution; silver-loaded nanocarbon black, polyvinyl pyrrolidone and deionized water are mixed in a mass ratio of 1: (0.5-1.5): (35-45), stirred at 200-300 rpm for 23-25 hours, 130-140 times the mass of the silver-loaded nanocarbon black and a volume fraction of 3%-5% ammonia alcohol solution are added, and 45-55 times the mass of the silver-loaded nanocarbon black is added at a uniform rate within 3-5 hours. The mixture is stirred for 2-4 hours and then filtered, washed with deionized water and anhydrous ethanol for 3-5 times respectively, and dried at 100-110°C for 23-25 hours to obtain transparent silicon-coated carbon black;

[0014] (3) Transparent silicon-coated carbon black, ethyl hypophosphite and deionized water were mixed in a mass ratio of 1: (1.2-1.4): (20-30), stirred at 60-70°C and 100-200 rpm for 12-14 hours, naturally cooled to room temperature and filtered, washed with deionized water for 3-5 times, and dried at 75-85°C for 8-10 hours to obtain modified transparent silicon-coated carbon black; modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene, 5-allyl -3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene are mixed in a mass ratio of 1:(0.7-0.9):(2.2-2.4):(0.01-0.03):(5-7), stirred in a nitrogen atmosphere at 80-90°C and 270-290r / min for 9-11 hours, naturally cooled to room temperature and then filtered, washed with anhydrous ethanol 3-5 times, and dried at 60-70°C for 23-25 hours to obtain an anti-aging flame retardant black disperse dye.

[0015] As an optimization, the reaction equation of the silver-loaded nanocarbon black in step (1) is:

[0016]

[0017] As an optimization, the reaction equation of the transparent silicon encapsulated carbon black in step (2) is:

[0018]

[0019] in for As an optimization, the reaction equation for the modified transparent silicon-wrapped carbon black in step (3) is:

[0020]

[0021] in for As an optimization, the reaction equation of the anti-aging flame retardant black disperse dye in step (3) is:

[0022] in for

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The present invention prepares the anti-aging flame-retardant black disperse dye by: oxidizing nano carbon black with nitric acid and reacting it with silver nitrate to obtain silver-loaded nano carbon black; polymerizing ethyl orthosilicate and 3-chloropropyltrimethoxysilane on the surface of the silver-loaded nano carbon black to obtain transparent silicon-wrapped carbon black; reacting the transparent silicon-wrapped carbon black with ethyl hypophosphite to obtain modified transparent silicon-wrapped carbon black; and finally reacting the modified transparent silicon-wrapped carbon black, 3,4-epoxy-1-butene and methyl 5-allyl-3-methoxysalicylate to obtain the anti-aging flame-retardant black disperse dye.

[0025] First, nano-carbon black is oxidized with nitric acid and then reacted with silver nitrate to obtain silver-loaded nano-carbon black; ethyl orthosilicate and 3-chloropropyltrimethoxysilane are polymerized on the surface of the silver-loaded nano-carbon black to obtain transparent silicon-coated carbon black; the nano-carbon black is oxidized with nitric acid to increase the content of active groups such as carboxyl and hydroxyl groups on the surface of the nano-carbon black, increase the loading amount of silver ions, and improve the antibacterial properties of the anti-aging and flame-retardant black disperse dye; by polymerizing a layer of transparent silicon on the surface of the silver-loaded nano-carbon black, the aggregation of carbon black in the matrix is effectively reduced, and at the same time, the carbon black can be protected from external damage, thereby improving the wear resistance of the anti-aging and flame-retardant black disperse dye.

[0026] Secondly, transparent silicon-wrapped carbon black and ethyl hypophosphite are reacted to obtain modified transparent silicon-wrapped carbon black; then the modified transparent silicon-wrapped carbon black, 3,4-epoxy-1-butene and 5-allyl-3-methoxysalicylic acid methyl ester are reacted to obtain anti-aging flame-retardant black disperse dye; by introducing chlorine atoms into the transparent silicon layer and grafting ethyl hypophosphite, it can be decomposed to generate phosphoric acid, metaphosphoric acid, etc. at high temperature, promoting the dehydration and carbonization of the polymer to form a non-flammable carbon layer, isolating heat and oxygen, preventing the spread of flames, and improving the anti-aging resistance. The flame retardant black disperse dye is flame retardant; by using the addition of phosphorus and hydrogen to the carbon-carbon double bond, 3,4-epoxy-1-butene and 5-allyl-3-methoxysalicylic acid methyl ester are grafted on the outer layer. The epoxy group can react with the carboxyl group to enhance the chemical bonding with the acrylic resin adhesive and improve the wear resistance of the anti-aging and flame retardant black disperse dye; the grafting of 5-allyl-3-methoxysalicylic acid methyl ester can scavenge free radicals, inhibit the generation of free radicals, and absorb ultraviolet rays, further improving the anti-aging performance of the anti-aging and flame retardant black disperse dye. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0028] Example 1:

[0029] A method for preparing an anti-aging flame-retardant black disperse dye, comprising the following steps:

[0030] (1) Nano-carbon black and nitric acid solution with a mass fraction of 67% were mixed in a mass ratio of 1:9, ultrasonically dispersed for 25 minutes, stirred and refluxed at 75°C and 100 rpm for 4 hours, cooled naturally to room temperature, and then the upper acid solution was poured out. The mixture was washed with deionized water 3 times and dried at 105°C for 5 hours to obtain oxidized carbon black; oxidized carbon black and deionized water were mixed in a mass ratio of 1:199, ultrasonically dispersed at 20°C for 20 minutes, and 0.1 mol / L silver nitrate solution (150 times the mass of oxidized carbon black) was added to adjust the solution pH to 6. The mixture was stirred at 60°C and 200 rpm for 6 hours, cooled naturally to room temperature, filtered, washed with deionized water 3 times, and dried at 115°C for 5 hours to obtain silver-loaded nano-carbon black;

[0031] (2) Ethyl orthosilicate, 3-chloropropyltrimethoxysilane and anhydrous ethanol were mixed in a mass ratio of 1:0.9:7 to obtain a silicon source mixture; silver-loaded nanocarbon black, polyvinyl pyrrolidone and deionized water were mixed in a mass ratio of 1:0.5:35, stirred at 20°C and 200 rpm for 25 hours, and a 3% ammonia alcohol solution with a volume fraction of 130 times the mass of the silver-loaded nanocarbon black was added, and the silicon source mixture with a volume fraction of 45 times the mass of the silver-loaded nanocarbon black was added at a uniform rate within 3 hours. After stirring for 4 hours, the mixture was filtered, washed with deionized water and anhydrous ethanol three times respectively, and dried at 100°C for 25 hours to obtain transparent silicon-coated carbon black;

[0032] (3) Transparent silicon-coated carbon black, ethyl hypophosphite and deionized water were mixed in a mass ratio of 1:1.2:20, stirred at 60°C and 100 rpm for 14 h, naturally cooled to room temperature and filtered, washed with deionized water three times, and dried at 75°C for 10 h to obtain modified transparent silicon-coated carbon black; modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene, 5-allyl-3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene were mixed in a mass ratio of 1:0.7:2.2:0.01:5, stirred at 80°C and 270 r / min in a nitrogen atmosphere for 11 h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol three times, and dried at 60°C for 25 h to obtain anti-aging flame-retardant black disperse dye.

[0033] Example 2:

[0034] A method for preparing an anti-aging flame-retardant black disperse dye, comprising the following steps:

[0035] (1) Nano-carbon black and nitric acid solution with a mass fraction of 68% were mixed in a mass ratio of 1:10, ultrasonically dispersed for 30 minutes, stirred and refluxed at 80°C and 150 rpm for 3 hours, cooled naturally to room temperature, poured out the upper acid solution, washed with deionized water 4 times, and dried at 110°C for 4 hours to obtain oxidized carbon black; oxidized carbon black and deionized water were mixed in a mass ratio of 1:200, ultrasonically dispersed at 25°C for 15 minutes, 0.2 mol / L silver nitrate solution (200 times the mass of oxidized carbon black) was added, the pH of the solution was adjusted to 6.5, stirred at 65°C and 250 rpm for 5.5 hours, cooled naturally to room temperature, filtered, washed with deionized water 4 times, and dried at 120°C for 4 hours to obtain silver-loaded nano-carbon black;

[0036] (2) Ethyl orthosilicate, 3-chloropropyltrimethoxysilane and anhydrous ethanol were mixed in a mass ratio of 1:1:8 to obtain a silicon source mixture; silver-loaded nanocarbon black, polyvinyl pyrrolidone and deionized water were mixed in a mass ratio of 1:1:40, stirred at 25°C and 250 rpm for 24 hours, and a 4% ammonia alcohol solution with a volume fraction of 135 times the mass of the silver-loaded nanocarbon black was added, and the silicon source mixture with a volume fraction of 50 times the mass of the silver-loaded nanocarbon black was added at a uniform rate within 4 hours. After stirring for 3 hours, the mixture was filtered, washed with deionized water and anhydrous ethanol four times respectively, and dried at 105°C for 24 hours to obtain transparent silicon-coated carbon black;

[0037] (3) Transparent silicon-coated carbon black, ethyl hypophosphite and deionized water were mixed in a mass ratio of 1:1.3:25, stirred at 65°C and 150 rpm for 13 h, naturally cooled to room temperature and filtered, washed with deionized water 4 times, and dried at 80°C for 9 h to obtain modified transparent silicon-coated carbon black; modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene, 5-allyl-3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene were mixed in a mass ratio of 1:0.8:2.3:0.02:6, stirred at 85°C and 280 r / min in a nitrogen atmosphere for 10 h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, and dried at 65°C for 24 h to obtain anti-aging flame-retardant black disperse dye.

[0038] Example 3:

[0039] A method for preparing an anti-aging flame-retardant black disperse dye, comprising the following steps:

[0040] (1) Nano-carbon black and nitric acid solution with a mass fraction of 69% were mixed in a mass ratio of 1:11, ultrasonically dispersed for 35 minutes, stirred and refluxed at 85°C and 200 rpm for 2 hours, cooled naturally to room temperature, and then the upper acid solution was poured out. The mixture was washed with deionized water 5 times and dried at 115°C for 3 hours to obtain oxidized carbon black; oxidized carbon black and deionized water were mixed in a mass ratio of 1:201, ultrasonically dispersed at 30°C for 10 minutes, and 0.3 mol / L silver nitrate solution (250 times the mass of oxidized carbon black) was added to adjust the solution pH to 7. The mixture was stirred at 70°C and 300 rpm for 5 hours, cooled naturally to room temperature, filtered, washed with deionized water 5 times, and dried at 125°C for 3 hours to obtain silver-loaded nano-carbon black;

[0041] (2) Ethyl orthosilicate, 3-chloropropyltrimethoxysilane and anhydrous ethanol were mixed in a mass ratio of 1:1.1:9 to obtain a silicon source mixture; silver-loaded nanocarbon black, polyvinyl pyrrolidone and deionized water were mixed in a mass ratio of 1:1.5:45, stirred at 30°C and 300 rpm for 23 hours, and a 5% ammonia alcohol solution with a volume fraction of 140 times the mass of the silver-loaded nanocarbon black was added. The silicon source mixture with a volume fraction of 55 times the mass of the silver-loaded nanocarbon black was added at a uniform rate within 5 hours. The mixture was stirred for 2 hours and then filtered. The mixture was washed with deionized water and anhydrous ethanol for 5 times respectively, and dried at 110°C for 23 hours to obtain transparent silicon-coated carbon black;

[0042] (3) Transparent silicon-coated carbon black, ethyl hypophosphite and deionized water were mixed in a mass ratio of 1:1.4:30, stirred at 70°C and 200 rpm for 12 h, naturally cooled to room temperature and filtered, washed with deionized water 5 times, and dried at 85°C for 8 h to obtain modified transparent silicon-coated carbon black; modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene, 5-allyl-3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene were mixed in a mass ratio of 1:0.9:2.4:0.03:7, stirred at 90°C and 290 r / min in a nitrogen atmosphere for 9 h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 5 times, and dried at 70°C for 23 h to obtain anti-aging flame-retardant black disperse dye.

[0043] Comparative Example 1:

[0044] A method for preparing an anti-aging flame-retardant black disperse dye, comprising the following steps:

[0045] (1) Ethyl orthosilicate, 3-chloropropyltrimethoxysilane and anhydrous ethanol were mixed in a mass ratio of 1:1:8 to obtain a silicon source mixture; nano carbon black, polyvinyl pyrrolidone and deionized water were mixed in a mass ratio of 1:1:40, stirred at 25°C and 250 rpm for 24 hours, and a 4% ammonia alcohol solution with a volume fraction of 135 times the mass of nano carbon black was added. The silicon source mixture with a volume fraction of 50 times the mass of nano carbon black was added at a uniform rate within 4 hours. The mixture was stirred for 3 hours and then filtered. The mixture was washed with deionized water and anhydrous ethanol for 4 times respectively, and dried at 105°C for 24 hours to obtain transparent silicon-coated carbon black;

[0046] (2) Transparent silicon-coated carbon black, ethyl hypophosphite and deionized water were mixed in a mass ratio of 1:1.3:25, stirred at 65°C and 150 rpm for 13 h, naturally cooled to room temperature and filtered, washed with deionized water 4 times, and dried at 80°C for 9 h to obtain modified transparent silicon-coated carbon black; modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene, 5-allyl-3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene were mixed in a mass ratio of 1:0.8:2.3:0.02:6, stirred at 85°C and 280 r / min in a nitrogen atmosphere for 10 h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, and dried at 65°C for 24 h to obtain anti-aging flame-retardant black disperse dye.

[0047] Comparative Example 2:

[0048] A method for preparing an anti-aging flame-retardant black disperse dye, comprising the following steps:

[0049] (1) Nano-carbon black and nitric acid solution with a mass fraction of 68% were mixed in a mass ratio of 1:10, ultrasonically dispersed for 30 minutes, stirred and refluxed at 80°C and 150 rpm for 3 hours, cooled naturally to room temperature, poured out the upper acid solution, washed with deionized water 4 times, and dried at 110°C for 4 hours to obtain oxidized carbon black; oxidized carbon black and deionized water were mixed in a mass ratio of 1:200, ultrasonically dispersed at 25°C for 15 minutes, 0.2 mol / L silver nitrate solution (200 times the mass of oxidized carbon black) was added, the pH of the solution was adjusted to 6.5, stirred at 65°C and 250 rpm for 5.5 hours, cooled naturally to room temperature, filtered, washed with deionized water 4 times, and dried at 120°C for 4 hours to obtain silver-loaded nano-carbon black;

[0050] (2) Ethyl orthosilicate, 3-chloropropyltrimethoxysilane and anhydrous ethanol were mixed in a mass ratio of 1:1:8 to obtain a silicon source mixture; silver-loaded nanocarbon black, polyvinyl pyrrolidone and deionized water were mixed in a mass ratio of 1:1:40, stirred at 25°C and 250 rpm for 24 hours, and a 4% ammonia alcohol solution with a volume fraction of 135 times the mass of the silver-loaded nanocarbon black was added, and the silicon source mixture with a volume fraction of 50 times the mass of the silver-loaded nanocarbon black was added at a uniform rate within 4 hours. After stirring for 3 hours, the mixture was filtered, washed with deionized water and anhydrous ethanol four times respectively, and dried at 105°C for 24 hours to obtain transparent silicon-coated carbon black;

[0051] (3) Transparent silicon-coated carbon black, ethyl hypophosphite and deionized water were mixed in a mass ratio of 1:1.3:25, stirred at 65°C and 150 rpm for 13 h, naturally cooled to room temperature and filtered, washed with deionized water 4 times, and dried at 80°C for 9 h to obtain modified transparent silicon-coated carbon black; modified transparent silicon-coated carbon black, 5-allyl-3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene were mixed in a mass ratio of 1:4.6:0.02:6, stirred at 85°C and 280 r / min for 10 h in a nitrogen atmosphere, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, and dried at 65°C for 24 h to obtain anti-aging flame-retardant black disperse dye.

[0052] Comparative Example 3:

[0053] A method for preparing an anti-aging flame-retardant black disperse dye, comprising the following steps:

[0054] (1) Nano-carbon black and nitric acid solution with a mass fraction of 68% were mixed in a mass ratio of 1:10, ultrasonically dispersed for 30 minutes, stirred and refluxed at 80°C and 150 rpm for 3 hours, cooled naturally to room temperature, poured out the upper acid solution, washed with deionized water 4 times, and dried at 110°C for 4 hours to obtain oxidized carbon black; oxidized carbon black and deionized water were mixed in a mass ratio of 1:200, ultrasonically dispersed at 25°C for 15 minutes, 0.2 mol / L silver nitrate solution (200 times the mass of oxidized carbon black) was added, the pH of the solution was adjusted to 6.5, stirred at 65°C and 250 rpm for 5.5 hours, cooled naturally to room temperature, filtered, washed with deionized water 4 times, and dried at 120°C for 4 hours to obtain silver-loaded nano-carbon black;

[0055] (2) Ethyl orthosilicate, 3-chloropropyltrimethoxysilane and anhydrous ethanol were mixed in a mass ratio of 1:1:8 to obtain a silicon source mixture; silver-loaded nanocarbon black, polyvinyl pyrrolidone and deionized water were mixed in a mass ratio of 1:1:40, stirred at 25°C and 250 rpm for 24 hours, and a 4% ammonia alcohol solution with a volume fraction of 135 times the mass of the silver-loaded nanocarbon black was added, and the silicon source mixture with a volume fraction of 50 times the mass of the silver-loaded nanocarbon black was added at a uniform rate within 4 hours. After stirring for 3 hours, the mixture was filtered, washed with deionized water and anhydrous ethanol four times respectively, and dried at 105°C for 24 hours to obtain transparent silicon-coated carbon black;

[0056] (3) Transparent silicon-coated carbon black, ethyl hypophosphite and deionized water were mixed in a mass ratio of 1:1.3:25, stirred at 65°C and 150 rpm for 13 h, naturally cooled to room temperature and filtered, washed with deionized water 4 times, and dried at 80°C for 9 h to obtain modified transparent silicon-coated carbon black; modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene, azobisisobutyronitrile and toluene were mixed in a mass ratio of 1:1.6:0.02:6, stirred at 85°C and 280 r / min in a nitrogen atmosphere for 10 h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, and dried at 65°C for 24 h to obtain anti-aging flame-retardant black disperse dye.

[0057] Comparative Example 4:

[0058] A method for preparing an anti-aging flame-retardant black disperse dye, comprising the following steps:

[0059] (1) Nano-carbon black and nitric acid solution with a mass fraction of 68% were mixed in a mass ratio of 1:10, ultrasonically dispersed for 30 minutes, stirred and refluxed at 80°C and 150 rpm for 3 hours, cooled naturally to room temperature, poured out the upper acid solution, washed with deionized water 4 times, and dried at 110°C for 4 hours to obtain oxidized carbon black; oxidized carbon black and deionized water were mixed in a mass ratio of 1:200, ultrasonically dispersed at 25°C for 15 minutes, 0.2 mol / L silver nitrate solution (200 times the mass of oxidized carbon black) was added, the pH of the solution was adjusted to 6.5, stirred at 65°C and 250 rpm for 5.5 hours, cooled naturally to room temperature, filtered, washed with deionized water 4 times, and dried at 120°C for 4 hours to obtain silver-loaded nano-carbon black;

[0060] (2) Ethyl orthosilicate, allyl trimethoxysilane and anhydrous ethanol were mixed in a mass ratio of 1:1:8 to obtain a silicon source mixture; silver-loaded nanocarbon black, polyvinyl pyrrolidone and deionized water were mixed in a mass ratio of 1:1:40, stirred at 25°C and 250 rpm for 24 hours, and a 4% ammonia alcohol solution with a volume fraction of 135 times the mass of the silver-loaded nanocarbon black was added. The silicon source mixture with a volume fraction of 50 times the mass of the silver-loaded nanocarbon black was added at a uniform rate within 4 hours. The mixture was stirred for 3 hours and then filtered. The mixture was washed with deionized water and anhydrous ethanol for 4 times respectively, and dried at 105°C for 24 hours to obtain transparent silicon-coated carbon black;

[0061] (3) Transparent silicon-coated carbon black, 3,4-epoxy-1-butene, 5-allyl-3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene were mixed in a mass ratio of 1:0.8:2.3:0.02:6, stirred at 85°C and 280 r / min for 10 h in a nitrogen atmosphere, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, and dried at 65°C for 24 h to obtain an anti-aging flame retardant black disperse dye.

[0062] Comparative Example 5:

[0063] A method for preparing an anti-aging flame-retardant black disperse dye, comprising the following steps:

[0064] (1) Nano-carbon black and nitric acid solution with a mass fraction of 68% were mixed in a mass ratio of 1:10, ultrasonically dispersed for 30 minutes, stirred and refluxed at 80°C and 150 rpm for 3 hours, cooled naturally to room temperature, poured out the upper acid solution, washed with deionized water 4 times, and dried at 110°C for 4 hours to obtain oxidized carbon black; oxidized carbon black and deionized water were mixed in a mass ratio of 1:200, ultrasonically dispersed at 25°C for 15 minutes, 0.2 mol / L silver nitrate solution (200 times the mass of oxidized carbon black) was added, the pH of the solution was adjusted to 6.5, stirred at 65°C and 250 rpm for 5.5 hours, cooled naturally to room temperature, filtered, washed with deionized water 4 times, and dried at 120°C for 4 hours to obtain silver-loaded nano-carbon black;

[0065] (2) silver-loaded nanocarbon black, polyvinyl pyrrolidone and deionized water were mixed in a mass ratio of 1:1:40, stirred at 25°C and 250 rpm for 24 h, and a 4% ammonia alcohol solution with a volume fraction of 135 times the mass of the silver-loaded nanocarbon black was added. 3-chloropropyltrimethoxysilane with a volume fraction of 50 times the mass of the silver-loaded nanocarbon black was added at a uniform rate within 4 h. After stirring for 3 h, the mixture was filtered, washed with deionized water and anhydrous ethanol four times respectively, and dried at 105°C for 24 h to obtain pre-modified carbon black;

[0066] (3) Pre-modified carbon black, ethyl hypophosphite and deionized water were mixed in a mass ratio of 1:1.3:25, stirred at 65°C and 150 rpm for 13 h, naturally cooled to room temperature and filtered, washed with deionized water 4 times, and dried at 80°C for 9 h to obtain modified transparent silicon-coated carbon black; modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene, 5-allyl-3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene were mixed in a mass ratio of 1:0.8:2.3:0.02:6, stirred at 85°C and 280 r / min in a nitrogen atmosphere for 10 h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, and dried at 65°C for 24 h to obtain anti-aging flame-retardant black disperse dye.

[0067] Test Example 1:

[0068] The anti-aging flame-retardant black disperse dye obtained in each example and the comparative example were respectively mixed with a carboxyl-containing aqueous acrylic resin, deionized water, anhydrous ethanol, and triethylamine in a mass ratio of 1:1.5:0.8:0.4:0.3 to obtain a water-based ink. The ink was scraped onto a glass substrate using a wire rod applicator. After natural leveling, it was placed in a blast drying oven for drying and curing, and then peeled off to obtain an ink coating.

[0069] 1. Antibacterial properties

[0070] Test method: Take the same mass of the anti-aging flame retardant black disperse dye obtained in each example and the comparative example, stir them in deionized water for 4 hours, filter and dry them, sterilize them at 125℃ for 15 minutes, and then add deionized water to make a 5wt% suspension sample; under sterile conditions, pour the sterilized nutrient agar medium into a culture dish, cool it down, dig a hole in the middle of the culture medium with a 1cm diameter hole digger, add the base culture medium and let it stand and cool, add 100μL of 10% 6 Coli suspension (CFU / mL) was evenly scraped onto the surface of the cooled nutrient agar medium, and an equal amount of suspension sample was dropped into the wells. The suspension was cultured at 37°C for 24 h, and the width d1 of the inhibition zone was measured.

[0071] 2. Anti-aging

[0072] Test method: The ink coating obtained in each embodiment and the comparative example were cut into 80mm×30mm specimens respectively, and the breaking strength σ0 was tested using an AI-3000 universal tensile testing machine. According to GB / T16422 "Plastics Laboratory Light Source Exposure Test Method Part 3: Fluorescent UV Lamp" standard, ultraviolet artificial accelerated aging was carried out using the FR-1205-QUV ultraviolet aging tester of Shanghai Farui Instrument Technology Co., Ltd. After 7 days, the breaking strength σ1 was tested again, and the strength retention rate was calculated as σ1 / σ0*100%.

[0073] 3. Flame retardancy

[0074] Test method: The ink coatings obtained in each example and the comparative example were cut into samples of 135 mm × 50 mm in size, and the limiting oxygen index was tested according to GB / T2406.

[0075] 4. Wear resistance

[0076] Test method: Take the ink coating obtained in each example and the comparative example of the same size and weigh the mass m0, polish it 100 times with 400-grit sandpaper, and weigh the mass m1 again. Calculate the wear rate = m0-m1 / m0*100%.

[0077] Table 1 below shows the analysis results of the antibacterial, anti-aging, flame retardancy and wear resistance of the anti-aging flame retardant black disperse dyes of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0078] Table 1

[0079] Inhibition zone width cm Strength retention rate% Limiting oxygen index% Wear rate% Example 1 3.92 86.5 29.4 6.5 Example 2 3.96 87.4 29.7 6.7 Example 3 3.89 84.9 29.6 7.1 Comparative Example 1 0.24 83.4 29.3 9.7 Comparative Example 2 3.61 83.7 29.4 53.4 Comparative Example 3 3.82 56.1 29.2 10.2 Comparative Example 4 3.65 84.5 22.1 9.8 Comparative Example 5 3.37 81.8 28.6 41.7

[0080] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 1, it can be found that the anti-aging flame retardant black disperse dye prepared by the present invention has good antibacterial property, anti-aging property, flame retardancy and wear resistance.

[0081] By comparison, the width of the inhibition zone of Examples 1, 2, and 3 is larger than that of Comparative Example 1, which illustrates that the use of nitric acid to oxidize nano-carbon black increases the content of active groups such as carboxyl and hydroxyl groups on the surface of nano-carbon black, increases the loading amount of silver ions, and improves the antibacterial properties of the anti-aging and flame-retardant black disperse dye.

[0082] By comparison, the wear rates of Examples 1, 2, and 3 are lower than that of Comparative Example 2, indicating that by utilizing the addition of phosphorus and hydrogen to the carbon-carbon double bond and grafting 3,4-epoxy-1-butene on the outer layer, the epoxy group can react with the carboxyl group, thereby enhancing the chemical bonding with the acrylic resin adhesive and improving the wear resistance of the anti-aging flame-retardant black disperse dye.

[0083] By comparison, the strength retention rate of Examples 1, 2, and 3 is higher than that of Comparative Example 3, which shows that the use of phosphorus-hydrogen addition to carbon-carbon double bonds and grafting of 5-allyl-3-methoxysalicylate on the outer layer can scavenge free radicals, inhibit the generation of free radicals, absorb ultraviolet rays, and further improve the anti-aging properties of the anti-aging flame-retardant black disperse dye.

[0084] By comparison, the limiting oxygen index of Examples 1, 2, and 3 is higher than that of Comparative Example 4, which shows that by introducing chlorine atoms into the transparent silicon layer and grafting ethyl hypophosphite, it can be decomposed at high temperature to produce phosphoric acid, metaphosphoric acid, etc., promote the dehydration and carbonization of the polymer, form a non-flammable carbon layer, isolate heat and oxygen, prevent the spread of flame, and improve the flame retardancy of the anti-aging flame-retardant black disperse dye.

[0085] By comparison, the wear rates of Examples 1, 2, and 3 are lower than those of Comparative Example 5, indicating that by polymerizing a transparent silicon layer on the surface of the silver-loaded nanocarbon black, the aggregation of carbon black in the matrix is effectively reduced, while also protecting the carbon black from external damage, thereby improving the wear resistance of the anti-aging and flame-retardant black disperse dye.

[0086] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing an anti-aging flame retardant black disperse dye, characterized in that: The anti-aging flame-retardant black disperse dye is obtained by reacting modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene and 5-allyl-3-methoxysalicylic acid methyl ester; The modified transparent silicon-coated carbon black is obtained by reacting transparent silicon-coated carbon black with ethyl hypophosphite; The transparent silicon-wrapped carbon black is obtained by polymerizing ethyl orthosilicate and 3-chloropropyltrimethoxysilane on the surface of silver-loaded nanocarbon black; The silver-loaded nano-carbon black is obtained by reacting nano-carbon black with silver nitrate after being oxidized by nitric acid; The method comprises the following preparation steps: (1) Oxidizing nano-carbon black to obtain oxidized carbon black; mixing the oxidized carbon black and deionized water, ultrasonically dispersing them at 20-30°C for 10-20 min, adding silver nitrate solution 150-250 times the mass of the oxidized carbon black, adjusting the pH of the solution to 6-7, stirring at 60-70°C and 200-300 rpm for 5-6 h, naturally cooling to room temperature and filtering, washing with deionized water 3-5 times, and drying at 115-125°C for 3-5 h to obtain silver-loaded nano-carbon black; (2) Mix silver-loaded nanocarbon black, polyvinyl pyrrolidone and deionized water, stir at 20-30°C and 200-300 rpm for 23-25 hours, add an ammonia alcohol solution with a mass of 130-140 times that of the silver-loaded nanocarbon black, and uniformly add a silicon source mixed solution with a mass of 45-55 times that of the silver-loaded nanocarbon black within 3-5 hours, continue stirring for 2-4 hours, filter, wash with deionized water and anhydrous ethanol for 3-5 times respectively, and dry at 100-110°C for 23-25 hours to obtain transparent silicon-coated carbon black; (3) Transparent silicon-coated carbon black, ethyl hypophosphite and deionized water were mixed, stirred at 60-70°C and 100-200 rpm for 12-14 hours, naturally cooled to room temperature and filtered, washed with deionized water for 3-5 times, and dried at 75-85°C for 8-10 hours to obtain modified transparent silicon-coated carbon black; modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene, 5-allyl-3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene were mixed, stirred in a nitrogen atmosphere at 80-90°C for 9-11 hours, naturally cooled to room temperature and filtered, washed with anhydrous ethanol for 3-5 times, and dried at 60-70°C for 23-25 hours to obtain anti-aging flame-retardant black disperse dye.

2. The method for preparing an anti-aging flame retardant black disperse dye according to claim 1, wherein: The oxidation step in step (1) is as follows: nano carbon black and nitric acid solution with a mass fraction of 67% to 69% are mixed in a mass ratio of 1:(9 to 11), ultrasonically dispersed for 25 to 35 minutes, stirred and refluxed at 75 to 85°C and 100 to 200 rpm for 2 to 4 hours, naturally cooled to room temperature and then the upper layer of acid solution is poured out, washed with deionized water for 3 to 5 times, and dried at 105 to 115°C for 3 to 5 hours.

3. The method for preparing an anti-aging flame retardant black disperse dye according to claim 1, wherein: The concentration of the silver nitrate solution in step (1) is 0.1-0.3 mol / L.

4. The method for preparing an anti-aging flame retardant black disperse dye according to claim 1, wherein: In step (2), the silver-loaded nano-carbon black, polyvinyl pyrrolidone and deionized water are mixed in a mass ratio of 1:(0.5-1.5):(35-45).

5. The method for preparing an anti-aging flame retardant black disperse dye according to claim 1, wherein: The volume fraction of the ammonia alcohol solution in step (2) is 3% to 5%.

6. The method for preparing an anti-aging flame-retardant black disperse dye according to claim 1, wherein: The silicon source mixed solution in step (2) is obtained by mixing ethyl orthosilicate, 3-chloropropyltrimethoxysilane and anhydrous ethanol in a mass ratio of 1:(0.9~1.1):(7~9).

7. The method for preparing an anti-aging flame retardant black disperse dye according to claim 1, wherein: In step (3), the transparent silicon-coated carbon black, ethyl hypophosphite and deionized water are mixed in a mass ratio of 1:(1.2-1.4):(20-30).

8. The method for preparing an anti-aging flame-retardant black disperse dye according to claim 1, characterized in that: In step (3), the modified transparent silicon-coated carbon black, 3,4-epoxy-1-butene, 5-allyl-3-methoxysalicylic acid methyl ester, azobisisobutyronitrile and toluene are mixed in a mass ratio of 1:0.8:2.3:0.02:

6.

9. The method for preparing an anti-aging flame-retardant black disperse dye according to claim 1, wherein: The rotation speed of the stirring reaction in step (3) is 270~290r / min.

10. An anti-aging flame retardant black disperse dye prepared according to the preparation method of the anti-aging flame retardant black disperse dye according to any one of claims 1 to 9.

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