PET (Polyethylene Terephthalate) color master batch containing ultra-dispersed carbon black and preparation method of PET color master batch

Abstract

The invention relates to the technical field of plastic master batches, in particular to a PET (Polyethylene Terephthalate) color master batch containing ultra-dispersed carbon black and a preparation method of the PET color master batch. The preparation method comprises the following steps: firstly, adding gamma-methacryloxypropyltrimethoxysilane, carbon black powder, a dopamine solution and a titanium reaction solution to obtain a modified titanium dioxide coated carbon black material; and adding thiohydracrylic acid, diethanol amine, dimethylaminoethyl methacrylate and epoxy chloropropane to obtain the thiolated antibacterial substance. 3-bromo-1-propanol, methacryloyl chloride and triphenylphosphine are added, so that the quaternary phosphonium antibacterial substance is obtained. Finally, polyethylene glycol terephthalate, the modified titanium dioxide coated carbon black material, a sulfhydrylation antibacterial substance, a quaternary phosphonium antibacterial substance and a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone are used as main raw materials, and a finished product is prepared. The finished product prepared by the invention has excellent antibacterial property and color uniformity, so that the finished product has a wide application prospect in the technical field of plastic master batches.

Description

Technical Field

[0001] The invention relates to the technical field of plastic masterbatches, in particular to a PET masterbatch containing ultra-dispersed carbon black and a preparation method thereof. Background Art

[0002] PET masterbatches play a vital role in modern industry and life, demonstrating multi-dimensional value. From a manufacturing perspective, PET masterbatches significantly improve production efficiency. Traditional dyeing methods are cumbersome, while PET masterbatches can be quickly colored by simply adding the appropriate amount of colorant during processing, saving time and labor costs. PET masterbatches also contribute significantly to environmental protection. Traditional dyeing processes often produce large amounts of wastewater, exhaust gas, and other pollutants, causing serious environmental damage. Masterbatch production, on the other hand, is relatively clean and produces virtually no polluting waste during use. PET masterbatches also drive product innovation and diversification. They can be blended into a rich variety of colors to meet the personalized aesthetic needs of diverse consumers. Whether it's a stylish electronic product casing or vibrant packaging, PET masterbatches provide unique color solutions.

[0003] PET materials are widely used in daily life, but bacterial growth can cause discoloration, deterioration, and odor in PET products, impacting their appearance and performance. Improving antimicrobial properties can effectively prevent these issues, extend product lifespan, improve product quality and stability, and reduce damage caused by bacterial attack. Furthermore, carbon black is often added as a colorant in PET masterbatches. Inhomogeneous dispersion of carbon black can easily lead to varying shades of color in the PET masterbatch. In plastic product processing, these color variations can cause appearance defects such as color spots and streaks in the final product, seriously impacting its aesthetics and quality. However, ultra-dispersible carbon black can be evenly distributed within the PET matrix, resulting in a consistent, pure black color for both the masterbatch and the final product, meeting the stringent color quality requirements of high-end products.

[0004] In order to overcome the defects of the prior art, the present invention provides a PET masterbatch containing ultra-dispersed carbon black and a preparation method thereof. Summary of the Invention

[0005] The object of the present invention is to provide a PET masterbatch containing ultra-dispersed carbon black and a preparation method thereof, so as to solve the problems raised in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions: A method for preparing a PET masterbatch containing ultra-dispersed carbon black comprises the following steps: Step one: add γ-methacryloxypropyl trimethoxysilane to deionized water, after stirring well, add titanium dioxide coated carbon black material, continue to stir at 25-30℃ for 6-8h, then centrifuge, wash with water, dry to obtain modified titanium dioxide coated carbon black material; Step two: mix mercaptopropionic acid and diethanolamine, react at 70-75℃ for 25-30h, after the reaction is completed, distill under reduced pressure to obtain mercapto reactive monomer; dissolve dimethylaminoethyl methacrylate in ethanol to obtain reaction liquid 1; dissolve epichlorohydrin in methanol to obtain reaction liquid 2; slowly drop reaction liquid 2 into reaction liquid 1, react at 45-50℃ for 8-10h, after the reaction is completed, distill under reduced pressure, wash, vacuum dry to obtain quaternary ammonium product; add quaternary ammonium product, mercapto reactive monomer to 2-3wt% acetic acid solution, react at 80-85℃ for 8-10h, after the reaction is completed, distill under reduced pressure, wash, dry to obtain mercapto antibacterial material; Step three: add bromination product, triphenylphosphine, hydroquinone to acetonitrile, after stirring well, stir at 75-80℃ for 55-65h, after the reaction is completed, rotary evaporate, vacuum dry to obtain quaternary phosphonium antibacterial material; Step four: blend polyethylene terephthalate, modified titanium dioxide coated carbon black material, mercapto antibacterial material, quaternary phosphonium antibacterial material, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, under the ultraviolet light with wavelength of 300-365nm, mix for 8-10min, then add antioxidant, dispersant, dense in 160-170℃ for 8-10min, after the dense mixing is completed, extrude and granulate to obtain finished product.

[0007] More preferably, in step one, the mass ratio of γ-methacryloxypropyl trimethoxysilane and titanium dioxide coated carbon black material is 1: (3-4).

[0008] More preferably, the preparation process of titanium dioxide coated carbon black material is: immerse carbon black powder in dopamine solution with pH of 8.5-8.7, stir and disperse at 60-65℃ for 20-25h, after stirring is completed, centrifuge, wash, dry to obtain dopamine modified carbon black; then immerse dopamine modified carbon black in titanium reaction liquid, stir and disperse at 40-45℃ for 10-12h, after stirring is completed, centrifuge, wash, dry to obtain titanium dioxide coated carbon black material.

[0009] More preferably, titanium reaction liquid is composed of ammonium fluorotitanate with concentration of 20-22g / mL and boric acid solution with concentration of 19-20g / mL, the concentration of dopamine solution is 2-2.5g / mL.

[0010] More optimally, in step 2, when preparing the thiol reaction monomer, the reaction molar ratio of mercaptopropionic acid and diethanolamine is 1: (1.1-1.2); when preparing the quaternized product, the reaction molar ratio of dimethylaminoethyl methacrylate and epichlorohydrin is 1: (1.1-1.2); when preparing the thiol antibacterial substance, the molar ratio of the quaternized product and the thiol reaction monomer is (2.2-2.3): 1.

[0011] More optimally, in step three, the reaction molar ratio of the brominated product to triphenylphosphine is 1:(1.1-1.2).

[0012] More optimally, the preparation process of the brominated product is as follows: 3-bromo-1-propanol and triethylamine are added to dichloromethane, and after sufficient stirring, methacryloyl chloride is added dropwise in an ice bath at 0-2°C. After the addition is completed, the reaction is continued for 2-3 hours, and then the reaction is continued at 25-30°C for 20-22 hours. After the reaction is completed, the brominated product is obtained by rotary evaporation and vacuum drying.

[0013] More optimally, the reaction molar ratio of 3-bromo-1-propanol and methacryloyl chloride is 1:(1.1-1.2).

[0014] More optimally, in step four, the contents of the components of the finished product are: in parts by mass, 80-90 parts of polyethylene terephthalate, 10-15 parts of modified titanium dioxide-coated carbon black material, 12-18 parts of thiol-containing antibacterial substance, 5-8 parts of quaternized phosphonium-containing antibacterial substance, 0.5-0.8 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.3-0.5 parts of antioxidant, and 0.5-0.8 parts of dispersant; the antioxidant is antioxidant 1076; and the dispersant is calcium stearate.

[0015] Beneficial effects of the present invention: The application is characterized in that, in step one, firstly, carbon black powder, dopamine solution and titanium reaction solution are added to obtain a titanium dioxide coated carbon black material. In this step, the dispersibility of carbon black is effectively improved by coating titanium dioxide material on the surface of carbon black. In addition, the titanium dioxide material also has excellent photocatalytic antibacterial performance, so that it can play a good antibacterial effect after subsequent ultraviolet irradiation. Specifically, titanium dioxide is a semiconductor material with excellent photocatalytic performance. When irradiated by a specific wavelength of ultraviolet light, the titanium dioxide will generate photo-generated holes. These photo-generated holes can convert water molecules and oxygen in the surrounding environment into highly active hydroxyl radicals and superoxide anion radicals, thereby chemically reacting with the cell wall and cell membrane of bacteria, destroying the normal physiological function of bacteria, and thus having excellent antibacterial performance. Then, the titanium dioxide coated carbon black material is further modified using gamma-methacryloxypropyl trimethoxysilane to obtain a modified titanium dioxide coated carbon black material. This step further improves the dispersibility of carbon black and introduces carbon-carbon double bonds, and finally obtains the modified titanium dioxide coated carbon black material.

[0016] The application is characterized in that, in step two, mercaptopropionic acid, diethanolamine, dimethylaminoethyl methacrylate, epichlorohydrin and acetic acid solution are added to obtain a mercapto-antibacterial substance. The amide reaction occurs between mercaptopropionic acid and diethanolamine to obtain a mercapto-reactive monomer. The nucleophilic substitution reaction occurs between dimethylaminoethyl methacrylate and epichlorohydrin to obtain a quaternary ammonium product with excellent antibacterial performance. The ring-opening reaction occurs between the mercapto-reactive monomer and the quaternary ammonium product to obtain a mercapto-antibacterial substance. Therefore, a mercapto-antibacterial material is obtained by continuous reaction in step two. In step three, 3-bromo-1-propanol, triethylamine, methacryloyl chloride and triphenylphosphine are added to occur a nucleophilic substitution reaction to obtain a quaternary phosphonium antibacterial substance. The quaternary phosphonium antibacterial substance has excellent antibacterial performance and introduces carbon-carbon double bonds.

[0017] The application is characterized in that, in step four, polyethylene terephthalate, modified titanium dioxide coated carbon black material, mercapto-antibacterial substance, quaternary phosphonium antibacterial substance, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, antioxidant and dispersant are used as raw materials to prepare a PET color master batch containing super-dispersed carbon black. In this step, polyethylene terephthalate, modified titanium dioxide coated carbon black material, mercapto-antibacterial substance, quaternary phosphonium antibacterial substance and photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone are blended under the irradiation of ultraviolet light to occur a mercapto-ene click reaction, thereby effectively blending and dispersing the several reactants. Then, antioxidant and dispersant are further added, and high-temperature mixing, extrusion and granulation are performed to finally obtain the finished PET color master batch.

[0018] Under UV light, the thiol groups in the thiolated antimicrobial substance undergo a thiol-ene click reaction with the carbon-carbon double bonds in the quaternary phosphonium-containing antimicrobial substance and the modified titanium dioxide-coated carbon black material. This reaction is highly efficient, rapid, and selective, forming chemical bonds between the reactants in a short period of time, thereby achieving effective blending and dispersion. Furthermore, this process allows the modified titanium dioxide-coated carbon black material to be evenly dispersed in the polyethylene terephthalate matrix, avoiding the agglomeration that can occur with traditional blending methods and improving the dispersion uniformity of the material. The subsequent addition of a dispersant further reduces the surface tension between the particles, ensuring that the modified titanium dioxide-coated carbon black material and the like remain well dispersed in the PET matrix, thereby improving the color uniformity and stability of the masterbatch. Furthermore, the thiolated antimicrobial substance, the quaternary phosphonium-containing antimicrobial substance, and the modified titanium dioxide-coated carbon black material all possess excellent antimicrobial properties. Therefore, effectively blending these three antimicrobial materials can significantly enhance the antimicrobial properties of the finished product. DETAILED DESCRIPTION

[0019] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0020] Source of raw materials: Carbon black powder, model TNC2501, specific gravity 0.55g / cm³; polyethylene terephthalate, provided by Dongguan Weicai Plastic Raw Materials Co., Ltd., model K2012; based on mass, one part is 1g.

[0021] Example 1: Step 1: Immerse carbon black powder in a dopamine solution with a pH of 8.7, stir and disperse at 65°C for 25 hours, centrifuge, wash, and dry after stirring to obtain dopamine-modified carbon black; then immerse the dopamine-modified carbon black in a titanium reaction solution, stir and disperse at 45°C for 12 hours, centrifuge, wash, and dry after stirring to obtain a titanium dioxide-coated carbon black material; the titanium reaction solution consists of ammonium fluorotitanate with a concentration of 21 g / mL and a boric acid solution with a concentration of 19.5 g / mL, and the concentration of the dopamine solution is 2.3 g / mL; γ-Methacryloxypropyltrimethoxysilane was added to deionized water, and after thorough stirring, titanium dioxide-coated carbon black material was added, and stirring was continued at 30°C for 8 hours. The mixture was then centrifuged, washed with water, and dried to obtain a modified titanium dioxide-coated carbon black material. The reaction mass ratio of γ-Methacryloxypropyltrimethoxysilane to titanium dioxide-coated carbon black material was 1:3.5. Step two: mix mercaptopropionic acid and diethanolamine, react at 75℃ for 30h, after the reaction is completed, distill under reduced pressure to obtain the mercapto-reactive monomer; dissolve dimethylaminoethyl methacrylate in ethanol to obtain reaction liquid 1; dissolve epichlorohydrin in methanol to obtain reaction liquid 2; slowly add reaction liquid 2 to reaction liquid 1, react at 50℃ for 10h, after the reaction is completed, distill under reduced pressure, wash, and dry under vacuum to obtain the quaternized product; add the quaternized product and the mercapto-reactive monomer to a 3wt% acetic acid solution, react at 85℃ for 10h, after the reaction is completed, distill under reduced pressure, wash, and dry to obtain the mercapto-functional antibacterial substance; when preparing the mercapto-reactive monomer, the reaction molar ratio of mercaptopropionic acid and diethanolamine is 1:1.15; when preparing the quaternized product, the reaction molar ratio of dimethylaminoethyl methacrylate and epichlorohydrin is 1:1.15; when preparing the mercapto-functional antibacterial substance, the molar ratio of the quaternized product and the mercapto-reactive monomer is 2.25:1; Step three: add 3-bromo-1-propanol and triethylamine to dichloromethane, after stirring thoroughly, add methacryloyl chloride dropwise under ice bath conditions at 2℃, continue to react for 3h after the addition is completed, then continue to react at 30℃ for 22h, after the reaction is completed, spin dry, and dry under vacuum to obtain the brominated product; the reaction molar ratio of 3-bromo-1-propanol and methacryloyl chloride is 1:1.15; Add the brominated product, triphenylphosphine, and hydroquinone to acetonitrile, after stirring thoroughly, stir and react at 80℃ for 65h, after the reaction is completed, spin dry, and dry under vacuum to obtain the phosphonium-functional antibacterial substance; the reaction molar ratio of the brominated product and triphenylphosphine is 1:1.15; Step four: blend 90g polyethylene terephthalate, 15g modified titanium dioxide coated carbon black material, 18g mercapto-functional antibacterial substance, 8g phosphonium-functional antibacterial substance, 0.8g photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, add 0.5g antioxidant 1076 and 0.8g calcium stearate, mix under ultraviolet light at a wavelength of 365nm for 10min, then mill at 170℃ for 10min, after the milling is completed, extrude and pelletize to obtain the finished product.

[0022] Example 2: Step one: immerse carbon black powder in a dopamine solution with a pH of 8.6, stir and disperse at 62℃ for 22h, after the stirring is completed, centrifuge, wash, and dry to obtain dopamine-modified carbon black; then immerse the dopamine-modified carbon black in a titanium reaction liquid, stir and disperse at 42℃ for 11h, after the stirring is completed, centrifuge, wash, and dry to obtain titanium dioxide coated carbon black material; the titanium reaction liquid is composed of ammonium fluorotitanate with a concentration of 21g / mL and boric acid solution with a concentration of 19.5g / mL, and the concentration of the dopamine solution is 2.3g / mL; γ-Methacryloxypropyltrimethoxysilane was added to deionized water, and after thorough stirring, titanium dioxide-coated carbon black material was added, and stirring was continued at 27°C for 7 hours. The mixture was then centrifuged, washed with water, and dried to obtain a modified titanium dioxide-coated carbon black material. The reaction mass ratio of γ-Methacryloxypropyltrimethoxysilane to titanium dioxide-coated carbon black material was 1:3.5. Step 2: Mix mercaptopropionic acid and diethanolamine, react at 72°C for 27 hours, and distill under reduced pressure after the reaction to obtain a mercapto reaction monomer; dissolve dimethylaminoethyl methacrylate in ethanol to obtain reaction solution 1; dissolve epichlorohydrin in methanol to obtain reaction solution 2; slowly add reaction solution 2 dropwise to reaction solution 1, react at 47°C for 9 hours, and distill under reduced pressure, wash, and vacuum dry after the reaction to obtain a quaternized product; add the quaternized product and the mercapto reaction monomer to a 3wt% acetic acid solution, react at 82°C for 9 hours, and distill under reduced pressure, wash, and dry to obtain a mercapto antibacterial substance; when preparing the mercapto reaction monomer, the reaction molar ratio of mercaptopropionic acid and diethanolamine is 1:1.15; when preparing the quaternized product, the reaction molar ratio of dimethylaminoethyl methacrylate and epichlorohydrin is 1:1.15; when preparing the mercapto antibacterial substance, the molar ratio of the quaternized product and the mercapto reaction monomer is 2.25:1; Step 3: Add 3-bromo-1-propanol and triethylamine to dichloromethane, stir thoroughly, and then add methacryloyl chloride dropwise in an ice bath at 1°C. Continue the reaction for 2.5 hours after the addition is complete, and then continue the reaction at 27°C for 21 hours. After the reaction is complete, the product is rotary evaporated and vacuum dried to obtain a brominated product; the reaction molar ratio of 3-bromo-1-propanol to methacryloyl chloride is 1:1.15; The brominated product, triphenylphosphine, and hydroquinone were added to acetonitrile, stirred thoroughly, and reacted at 77°C for 60 hours. After the reaction, the product was rotary evaporated and vacuum dried to obtain a quaternary phosphonium antibacterial substance. The reaction molar ratio of the brominated product to triphenylphosphine was 1:1.15. Step 4: Blend 90g of polyethylene terephthalate, 15g of modified titanium dioxide-coated carbon black material, 18g of thiol-modified antibacterial substance, 8g of quaternary phosphonium-modified antibacterial substance, and 0.8g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, mix under ultraviolet light with a wavelength of 365nm for 9min, then add 0.5g of antioxidant 1076 and 0.8g of calcium stearate, and mix at 165°C for 9min. After mixing, extrusion granulation is performed to obtain the finished product.

[0023] Example 3: Step 1: Immerse carbon black powder in a dopamine solution with a pH of 8.5, stir and disperse at 60°C for 20 hours, centrifuge, wash, and dry after stirring to obtain dopamine-modified carbon black; then immerse the dopamine-modified carbon black in a titanium reaction solution, stir and disperse at 40°C for 10 hours, centrifuge, wash, and dry after stirring to obtain a titanium dioxide-coated carbon black material; the titanium reaction solution consists of ammonium fluorotitanate with a concentration of 21 g / mL and a boric acid solution with a concentration of 19.5 g / mL, and the concentration of the dopamine solution is 2.3 g / mL; γ-Methacryloxypropyltrimethoxysilane was added to deionized water, and after thorough stirring, titanium dioxide-coated carbon black material was added, and stirring was continued at 25°C for 6 hours. The mixture was then centrifuged, washed with water, and dried to obtain a modified titanium dioxide-coated carbon black material. The reaction mass ratio of γ-Methacryloxypropyltrimethoxysilane to titanium dioxide-coated carbon black material was 1:3.5. Step 2: Mix mercaptopropionic acid and diethanolamine, react at 70°C for 25 hours, and distill under reduced pressure after the reaction to obtain a mercapto reaction monomer; dissolve dimethylaminoethyl methacrylate in ethanol to obtain reaction solution 1; dissolve epichlorohydrin in methanol to obtain reaction solution 2; slowly add reaction solution 2 dropwise to reaction solution 1, react at 45°C for 8 hours, and distill under reduced pressure, wash, and vacuum dry after the reaction to obtain a quaternized product; add the quaternized product and the mercapto reaction monomer to a 3wt% acetic acid solution, react at 80°C for 8 hours, and distill under reduced pressure, wash, and dry to obtain a mercapto antibacterial substance; when preparing the mercapto reaction monomer, the reaction molar ratio of mercaptopropionic acid and diethanolamine is 1:1.15; when preparing the quaternized product, the reaction molar ratio of dimethylaminoethyl methacrylate and epichlorohydrin is 1:1.15; when preparing the mercapto antibacterial substance, the molar ratio of the quaternized product and the mercapto reaction monomer is 2.25:1; Step 3: Add 3-bromo-1-propanol and triethylamine to dichloromethane, stir thoroughly, and then add methacryloyl chloride dropwise in an ice bath at 0°C. Continue the reaction for 2 hours after the addition is complete, and then continue the reaction at 25°C for 20 hours. After the reaction is complete, perform rotary evaporation and vacuum drying to obtain a brominated product. The reaction molar ratio of 3-bromo-1-propanol to methacryloyl chloride is 1:1.15. The brominated product, triphenylphosphine, and hydroquinone were added to acetonitrile, stirred thoroughly, and reacted at 75°C for 55 hours. After the reaction, the product was rotary evaporated and vacuum dried to obtain a quaternary phosphonium antibacterial substance. The reaction molar ratio of the brominated product to triphenylphosphine was 1:1.15. Step four: blend 90 g of polyethylene terephthalate, 15 g of modified titanium dioxide coated carbon black material, 18 g of mercapto-antibacterial substance, 8 g of quaternary phosphonium-antibacterial substance, 0.8 g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and mix for 8 min under ultraviolet light of wavelength 365 nm, then add 0.5 g of antioxidant 1076 and 0.8 g of calcium stearate, and densify for 8 min at 160°C. After densification, extrude and pelletize to obtain the finished product.

[0024] Comparative example 1: replace the modified titanium dioxide coated carbon black material with carbon black powder, and the rest is the same as example 1. The specific steps are as follows: step one: mix mercaptopropionic acid and diethanolamine and react at 75°C for 30 h. After the reaction, distill under reduced pressure to obtain a mercapto-reacted monomer. Dissolve dimethylaminoethyl methacrylate in ethanol to obtain reaction solution 1. Dissolve epichlorohydrin in methanol to obtain reaction solution 2. Slowly add reaction solution 2 to reaction solution 1 and react at 50°C for 10 h. After the reaction, distill under reduced pressure, wash, and vacuum dry to obtain a quaternary ammonium product. Add the quaternary ammonium product and mercapto-reacted monomer to a 3 wt% acetic acid solution and react at 85°C for 10 h. After the reaction, distill under reduced pressure, wash, and dry to obtain a mercapto-antibacterial substance. The reaction molar ratio of mercaptopropionic acid to diethanolamine when preparing the mercapto-reacted monomer is 1:1.15. The reaction molar ratio of dimethylaminoethyl methacrylate to epichlorohydrin when preparing the quaternary ammonium product is 1:1.15. The molar ratio of quaternary ammonium product to mercapto-reacted monomer when preparing the mercapto-antibacterial substance is 2.25:1. Step two: add 3-bromo-1-propanol and triethylamine to dichloromethane, stir well, and then add methacryloyl chloride dropwise under ice bath conditions at 2°C. After the addition is complete, continue to react for 3 h, then continue to react at 30°C for 22 h. After the reaction, rotary evaporate, and vacuum dry to obtain a brominated product. The reaction molar ratio of 3-bromo-1-propanol to methacryloyl chloride is 1:1.15. Add the brominated product, triphenylphosphine, and hydroquinone to acetonitrile, stir well, and then stir and react at 80°C for 65 h. After the reaction, rotary evaporate, and vacuum dry to obtain a quaternary phosphonium-antibacterial substance. The reaction molar ratio of the brominated product to triphenylphosphine is 1:1.15. Step three: blend 90 g of polyethylene terephthalate, 15 g of carbon black powder, 18 g of mercapto-antibacterial substance, 8 g of quaternary phosphonium-antibacterial substance, and 0.8 g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and mix for 10 min under ultraviolet light of wavelength 365 nm. Then add 0.5 g of antioxidant 1076 and 0.8 g of calcium stearate, and densify for 10 min at 170°C. After densification, extrude and pelletize to obtain the finished product.

[0025] Comparative Example 2: The thiol antibacterial substance was removed, and the rest was the same as Example 1, and the specific steps were as follows: Step 1: The carbon black powder was immersed in a dopamine solution with a pH of 8.7, stirred and dispersed at 65°C for 25 hours, and after the stirring was completed, the mixture was centrifuged, washed, and dried to obtain dopamine-modified carbon black; the dopamine-modified carbon black was then immersed in a titanium reaction solution, stirred and dispersed at 45°C for 12 hours, and after the stirring was completed, the mixture was centrifuged, washed, and dried to obtain a titanium dioxide-coated carbon black material; the titanium reaction solution consisted of ammonium fluorotitanate with a concentration of 21 g / mL and a boric acid solution with a concentration of 19.5 g / mL, and the concentration of the dopamine solution was 2.3 g / mL; γ-Methacryloxypropyltrimethoxysilane was added to deionized water, and after thorough stirring, titanium dioxide-coated carbon black material was added, and stirring was continued at 30°C for 8 hours. The mixture was then centrifuged, washed with water, and dried to obtain a modified titanium dioxide-coated carbon black material. The reaction mass ratio of γ-Methacryloxypropyltrimethoxysilane to titanium dioxide-coated carbon black material was 1:3.5. Step 2: Add 3-bromo-1-propanol and triethylamine to dichloromethane, stir thoroughly, and then add methacryloyl chloride dropwise in an ice bath at 2°C. Continue the reaction for 3 hours after the addition is complete, and then continue the reaction at 30°C for 22 hours. After the reaction is complete, the product is rotary evaporated and vacuum dried to obtain a brominated product. The reaction molar ratio of 3-bromo-1-propanol to methacryloyl chloride is 1:1.15. The brominated product, triphenylphosphine, and hydroquinone were added to acetonitrile, stirred thoroughly, and reacted at 80°C for 65 hours. After the reaction, the mixture was subjected to rotary evaporation and vacuum drying to obtain a quaternary phosphonium antibacterial substance. The reaction molar ratio of the brominated product to triphenylphosphine was 1:1.15. Step 3: Blend 90g of polyethylene terephthalate, 15g of modified titanium dioxide-coated carbon black material, 8g of quaternary phosphonium antibacterial substance, and 0.8g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, mix for 10 minutes under ultraviolet light with a wavelength of 365nm, then add 0.5g of antioxidant 1076 and 0.8g of calcium stearate, and mix at 170°C for 10 minutes. After mixing, extrusion granulation is performed to obtain the finished product.

[0026] Comparative Example 3: The thiol antibacterial substance and the quaternary phosphonium antibacterial substance were removed, and the rest was the same as Example 1, and the specific steps were as follows: Step 1: The carbon black powder was immersed in a dopamine solution with a pH of 8.7, stirred and dispersed at 65°C for 25 hours, and after the stirring was completed, the mixture was centrifuged, washed, and dried to obtain dopamine-modified carbon black; the dopamine-modified carbon black was then immersed in a titanium reaction solution, stirred and dispersed at 45°C for 12 hours, and after the stirring was completed, the mixture was centrifuged, washed, and dried to obtain a titanium dioxide-coated carbon black material; the titanium reaction solution consisted of ammonium fluorotitanate with a concentration of 21 g / mL and a boric acid solution with a concentration of 19.5 g / mL, and the concentration of the dopamine solution was 2.3 g / mL; The γ-methacryloyloxypropyl trimethoxysilane was added into deionized water, and the titanium dioxide coated carbon black material was added after sufficient stirring, and stirring was continued at 30℃ for 8h, and then centrifugation, water washing and drying were performed to obtain the modified titanium dioxide coated carbon black material; the mass ratio of the γ-methacryloyloxypropyl trimethoxysilane and the titanium dioxide coated carbon black material was 1:3.5; Step two: 90g of polyethylene terephthalate, 15g of the modified titanium dioxide coated carbon black material, 0.8g of the photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone were blended, and mixing was performed under ultraviolet light with a wavelength of 365nm for 10min, and then 0.5g of antioxidant 1076 and 0.8g of calcium stearate were added, and internal mixing was performed at 170℃ for 10min, and then extrusion granulation was performed after the internal mixing to obtain the finished product.

[0027] Test experiment:

[0028] Antibacterial test: the finished product PET color master batch prepared in the application was subjected to hot pressing (temperature was 150℃) to obtain a PET film, and the PET film was used as a test sample; the test sample was placed in a culture dish of escherichia coli, and incubation was performed at 25℃ for 20h, and then the antibacterial circle diameter of the test sample was tested after the incubation.

[0029] Dispersion test: the modified titanium dioxide coated carbon black material or the carbon black powder used in the examples and the comparative examples of the application was used as a test sample, and the test sample was added into deionized water and left to stand for 5 months, and the state of the test sample in the deionized water was observed.

[0030] Stability test: the finished product PET color master batch prepared in the application was used as a test sample, and the surface state was observed after standing for 5 months, and the stability of the test sample was judged by the color change of the surface. The results are as follows:

[0031] Conclusion: the dosage of examples 1-3 was unchanged, and only part of the reaction parameters was modified. According to the experimental data, the performance of the test sample did not change significantly.

[0032] Comparative example 1: the modified titanium dioxide coated carbon black material was replaced by carbon black powder, and the rest was the same as example 1. According to the experimental data, compared with example 1, the antibacterial circle diameter was reduced to 1.05mm; the dispersion state was that the agglomeration was serious, and the dispersion was very poor; the surface state of the test sample was that the color was unstable, and there was obvious color difference; the reason was that the carbon black powder was easy to agglomerate, so the carbon black powder was coated with titanium dioxide and modified in sequence in the application, so as to improve the dispersion of the carbon black powder. Therefore, after the modified titanium dioxide coated carbon black material was replaced by the carbon black powder, the antibacterial property was reduced, the dispersion was poor, so the antibacterial circle diameter was reduced, the agglomeration was serious, and the PET color master batch had obvious color difference.

[0033] Comparative Example 2: The thiol antibacterial substance was removed, and the rest was the same as Example 1. It can be seen from the experimental data that compared with Example 1, the diameter of the inhibition zone was reduced to 0.98 mm; the dispersion state showed agglomeration, but the agglomeration was not obvious; the surface state of the sample showed partial color difference; the reasons were analyzed as follows: the thiol antibacterial substance prepared by the present invention has excellent antibacterial properties, and the thiol antibacterial substance can react chemically with the modified titanium dioxide-coated carbon black material and the quaternary phosphonium antibacterial substance, thereby further effectively dispersing the carbon black raw material. Therefore, after the thiol antibacterial substance is removed, the antibacterial property is reduced and the dispersibility becomes worse, so the diameter of the inhibition zone is reduced, there is agglomeration, and the PET masterbatch has partial color difference.

[0034] Comparative Example 3: The thiol antibacterial substance and the quaternary phosphonium antibacterial substance were removed, and the rest was the same as Example 1. From the experimental data, it can be seen that compared with Example 1, the diameter of the inhibition zone was reduced to 0.84 mm; the dispersion state showed agglomeration, but the agglomeration was not obvious; the surface state of the sample showed partial color difference; the reason for analysis was: Comparative Example 3 further removed the quaternary phosphonium antibacterial substance on the basis of Comparative Example 2, so the antibacterial activity was further reduced.

[0035] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "include," "comprise," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a process, method, article, or apparatus comprising a series of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0036] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing PET masterbatch containing ultra-dispersed carbon black, characterized in that: The following steps are involved: Step 1: Add γ-methacryloxypropyltrimethoxysilane to deionized water, stir thoroughly, then add titanium dioxide-coated carbon black material, continue stirring at 25-30°C for 6-8 hours, then centrifuge, wash with water, and dry to obtain a modified titanium dioxide-coated carbon black material; Step 2: Mix mercaptopropionic acid and diethanolamine, react at 70-75° C. for 25-30 hours, and distill under reduced pressure after the reaction to obtain a thiol reaction monomer; dissolve dimethylaminoethyl methacrylate in ethanol to obtain a reaction solution 1; dissolve epichlorohydrin in methanol to obtain a reaction solution 2; slowly add the reaction solution 2 dropwise to the reaction solution 1, react at 45-50° C. for 8-10 hours, and distill under reduced pressure, wash, and vacuum dry to obtain a quaternized product; add the quaternized product and the thiol reaction monomer to a 2-3wt% acetic acid solution, react at 80-85° C. for 8-10 hours, and distill under reduced pressure, wash, and dry to obtain a thiol antibacterial substance; Step 3: Add the brominated product, triphenylphosphine, and hydroquinone to acetonitrile, stir thoroughly, and react at 75-80°C for 55-65 hours. After the reaction is complete, perform rotary evaporation and vacuum drying to obtain a quaternary phosphonium antibacterial substance. Step 4: Blend polyethylene terephthalate, modified titanium dioxide-coated carbon black material, thiol antibacterial substance, quaternary phosphonium antibacterial substance, and photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, mix for 8-10 minutes under ultraviolet light with a wavelength of 300-365 nm, then add antioxidant and dispersant, and mix at 160-170° C. for 8-10 minutes. After mixing, granulate by extrusion to obtain the finished product.

2. The method for preparing a PET masterbatch containing ultra-dispersed carbon black according to claim 1, wherein: In step 1, the reaction mass ratio of γ-methacryloxypropyltrimethoxysilane and titanium dioxide-coated carbon black material is 1: (3-4).

3. The method for preparing a PET masterbatch containing ultra-dispersed carbon black according to claim 2, wherein: The preparation process of the titanium dioxide-coated carbon black material is as follows: immersing carbon black powder in a dopamine solution with a pH of 8.5-8.7, stirring and dispersing at 60-65°C for 20-25 hours, and then centrifuging, washing, and drying to obtain dopamine-modified carbon black. Then, the dopamine-modified carbon black is immersed in the titanium reaction solution, stirred and dispersed at 40-45° C. for 10-12 hours, and after stirring, centrifuged, washed, and dried to obtain a titanium dioxide-coated carbon black material.

4. The method for preparing a PET masterbatch containing ultra-dispersed carbon black according to claim 3, wherein: The titanium reaction solution consists of ammonium fluorotitanate with a concentration of 20-22 g / mL and a boric acid solution with a concentration of 19-20 g / mL, and the concentration of the dopamine solution is 2-2.5 g / mL.

5. The method for preparing a PET masterbatch containing ultra-dispersed carbon black according to claim 1, wherein: In step 2, when preparing the thiol-reactive monomer, the reaction molar ratio of mercaptopropionic acid and diethanolamine is 1:(1.1-1.2); when preparing the quaternized product, the reaction molar ratio of dimethylaminoethyl methacrylate and epichlorohydrin is 1:(1.1-1.2); when preparing the thiol-antibacterial substance, the molar ratio of the quaternized product and the thiol-reactive monomer is (2.2-2.3):

1.

6. The method for preparing a PET masterbatch containing ultra-dispersed carbon black according to claim 1, wherein: In step 3, the reaction molar ratio of the brominated product and triphenylphosphine is 1:(1.1-1.2).

7. The method for preparing a PET masterbatch containing ultra-dispersed carbon black according to claim 6, characterized in that: The preparation process of the brominated product is as follows: 3-bromo-1-propanol and triethylamine are added to dichloromethane, and after sufficient stirring, methacryloyl chloride is added dropwise in an ice bath at 0-2°C. After the addition is completed, the reaction is continued for 2-3 hours, and then the reaction is continued at 25-30°C for 20-22 hours. After the reaction is completed, the product is subjected to rotary evaporation and vacuum drying to obtain the brominated product.

8. The method for preparing a PET masterbatch containing ultra-dispersed carbon black according to claim 7, wherein: The reaction molar ratio of 3-bromo-1-propanol and methacryloyl chloride is 1:(1.1-1.2).

9. The method for preparing a PET masterbatch containing ultra-dispersed carbon black according to claim 1, wherein: In step four, the contents of the components of the finished product are: in parts by mass, 80-90 parts of polyethylene terephthalate, 10-15 parts of modified titanium dioxide-coated carbon black material, 12-18 parts of thiol antibacterial substance, 5-8 parts of quaternary phosphonium antibacterial substance, 0.5-0.8 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.3-0.5 parts of antioxidant, and 0.5-0.8 parts of dispersant; the antioxidant is antioxidant 1076; and the dispersant is calcium stearate.

10. A PET masterbatch containing super-dispersed carbon black, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 9.

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