Titanium nitride powder modified PET master batch and preparation method thereof

Abstract

The application discloses a titanium nitride powder modified PET master batch and a preparation method thereof, and relates to the technical field of high polymer materials.In the application, a high-temperature-resistant dispersant containing a benzene ring and a potassium sulfonate group is prepared, and is blended with titanium nitride powder to prepare a slurry, which improves the dispersing performance of titanium nitride in PET, and the introduction of the potassium sulfonate group enables the PET master batch obtained after blending and extrusion to have good antistatic ability, thereby improving the safety of the PET master batch.In addition, the PET master batch also contains an antibacterial ester compound, the molecular chain of the antibacterial ester compound contains a phenoxy ethanol antibacterial group and a triazine antibacterial group, and the two groups synergistically act to further improve the antibacterial property of the PET master batch, and the antibacterial ester compound has a high-temperature-resistant benzene ring and an ester bond, which is beneficial to improving the thermal decomposition temperature of the antibacterial group and the compatibility with PET, matches the high-temperature processing environment, and is beneficial to realizing long-acting antibacterial property.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a titanium nitride powder modified PET masterbatch and its preparation method. Background Technology

[0002] PET (polyethylene terephthalate) is a polyester obtained by polycondensation of terephthalic acid and ethylene glycol. It has good mechanical properties, barrier properties, and chemical stability, and is widely used in engineering plastics, films, packaging materials, and other fields. However, during daily use, PET surfaces are prone to static electricity, causing dust accumulation and potentially leading to short circuits in devices, or even accidents such as fires and explosions.

[0003] To avoid the above situation, it is necessary to prepare PET with excellent antistatic properties to improve safety. In traditional processes, antistatic fillers or antistatic agents are usually added directly, but problems such as uneven dispersion and poor durability still exist.

[0004] Therefore, the present invention provides a titanium nitride powder modified PET masterbatch and its preparation method to solve the problems mentioned above. Summary of the Invention

[0005] The purpose of this invention is to provide a titanium nitride powder modified PET masterbatch and its preparation method, which involves blending PET with titanium nitride to solve the problems mentioned in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing titanium nitride powder modified PET masterbatch, comprising the following processes: PET, titanium nitride slurry, antibacterial ester compound, and antioxidant are mixed, melted, extruded, and granulated to obtain titanium nitride powder modified PET masterbatch.

[0007] Furthermore, the mass ratio of PET, titanium nitride slurry, antibacterial ester compound and antioxidant is (55~75):(15~25):(10~18):(2~4).

[0008] Furthermore, the antioxidant is antioxidant 1010.

[0009] Furthermore, the titanium nitride slurry includes titanium nitride powder, a high-temperature resistant dispersant, and dipropylene glycol methyl ether acetate; The antibacterial ester compounds include phenoxyethanol antibacterial groups and triazine antibacterial groups.

[0010] Furthermore, the preparation process of the titanium nitride slurry is as follows: Step 1: Mix polyethylene glycol monoallyl ether and phthalic anhydride, heat to 95~100℃, add 4-dimethylaminopyridine, keep the reaction under nitrogen atmosphere, and distill under reduced pressure to obtain polyether ester containing double bonds. Step 2: Mix the double-bonded polyether ester, potassium propyl 3-sulfonate methacrylate, sodium hypophosphite, and deionized water, heat to 70-75°C, then add methacrylic acid and ammonium persulfate, and keep the reaction under nitrogen atmosphere. After the reaction is complete, cool and adjust the pH to 6-8 with NaOH solution to obtain a high-temperature resistant dispersant. Step 3: Mix titanium nitride powder, high-temperature resistant dispersant and dipropylene glycol methyl ether acetate, and ball mill to obtain titanium nitride slurry.

[0011] Furthermore, in step 1, the mass ratio of polyethylene glycol monoallyl ether, phthalic anhydride, and 4-dimethylaminopyridine is (8~10):(0.7~0.9):(0.10~0.20).

[0012] Furthermore, in step 1, the process conditions for the heat preservation reaction are: temperature 95~100℃, time 4~5h; The process conditions for vacuum distillation are: temperature 95~105℃, time 1.5~2.0h, and pressure 0.085~0.095MPa.

[0013] Furthermore, in step 2, the mass ratio of the polyether ester containing double bonds, potassium propyl 3-sulfonate methacrylate, sodium hypophosphite, deionized water, methacrylic acid, and ammonium persulfate is (20~26):(2.5~3.5):(0.10~0.15):(40~50):(1.2~1.6):(0.8~1.0).

[0014] Furthermore, in step 2, the NaOH solution has a mass fraction of 30%.

[0015] Furthermore, in step 2, the process conditions for the heat preservation reaction are: temperature 70~75℃, time 2~4h.

[0016] Furthermore, in step 3, the mass ratio of titanium nitride powder, high-temperature resistant dispersant, and dipropylene glycol methyl ether acetate is 20:(4~6):(65~75).

[0017] Furthermore, in step 3, the ball milling process conditions are: rotation speed 450~550 r / min, time 3~8 h; ball-to-material ratio is (3~5):1, and the ball milling medium is ZrO2.

[0018] In the above technical solution, in step 1, under the action of 4-dimethylaminopyridine, the terminal hydroxyl group of polyethylene glycol monoallyl ether undergoes a ring-opening reaction with phthalic anhydride to obtain a double-bonded polyether ester containing benzene rings and carboxyl groups; in step 2, under the action of ammonium persulfate, the double-bonded polyether ester, methacrylic acid, and potassium propyl methacrylate 3-sulfonate undergo free radical copolymerization to obtain a high-temperature resistant dispersant containing benzene rings, carboxyl groups, and potassium sulfonate groups; in step 3, through a ball milling process, the carboxyl groups and potassium sulfonate groups are adsorbed on the surface of titanium nitride powder to obtain titanium nitride slurry.

[0019] Furthermore, the preparation process of the antibacterial ester compound is as follows: S1: A hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid and 4-dimethylaminopyridine were mixed, and N,N-dimethylformamide and N,N'-diisopropylcarbodiimide were added under a nitrogen atmosphere and stirred to dissolve. The mixture was then heated to react and a double-bond-terminated ester compound was obtained. S2: Potassium propyl 3-sulfonate methacrylate, double-bond-terminated ester compounds, azobisisobutyronitrile, and anhydrous ethanol are mixed, heated, stirred, and reacted. After the reaction is completed, the mixture is rotary evaporated and dried to obtain antibacterial ester compounds.

[0020] Furthermore, in S1, the ratio of hydroxyl-capped antibacterial derivative, 4-vinylbenzoic acid, 4-dimethylaminopyridine, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide is 1 g : (0.5~0.7) g : (0.3~0.5) g : (2~4) mL : (2.0~2.4) mL.

[0021] Furthermore, in S1, the process conditions for the heating reaction are: temperature 68~72℃, time 10~12h.

[0022] Furthermore, in S2, the ratio of potassium propyl 3-sulfonate methacrylate, double-bond-terminated ester compounds, azobisisobutyronitrile, and anhydrous ethanol is (5~10) g : (20~30) g : (0.01~0.03) g : (500~800) mL.

[0023] Furthermore, in S2, the process conditions for the heating and stirring reaction are: temperature 65~70℃, time 3.5~4.0h, and rotation speed 200~300r / min; In S2, the rotary evaporation process conditions are: temperature 45~55℃, time 1.5~2.5h; In S2, the drying process conditions are: temperature 50~60℃, time 6~8h.

[0024] Furthermore, in S1, the hydroxyl-terminated antibacterial derivative is prepared by the following process: S1.1: Phenoxyethanol, cyanuric chloride and dichloromethane are mixed and stirred to dissolve. 2,4,6-trimethylpyridine is added and reacted at room temperature. After the reaction is completed, the mixture is extracted with deionized water and rotary evaporated to obtain the antibacterial derivative. S1.2: Mix the antibacterial derivative and dichloroethane, stir to dissolve, add 6-amino-1-hexanol, and heat under reflux to obtain the hydroxyl-terminated antibacterial derivative.

[0025] Furthermore, in S1.1, the ratio of phenoxyethanol, cyanuric chloride, dichloromethane and 2,4,6-trimethylpyridine is 1 g : (0.7~0.9) g : (13~17) mL : (0.8~1.0) mL.

[0026] Furthermore, in S1.1, the process conditions for the room temperature reaction are: temperature 22~26℃, time 5~7h; In S1.1, the process conditions for rotary evaporation are: temperature 30~35℃, time 30~50min.

[0027] Furthermore, in S1.2, the ratio of the antibacterial derivative, dichloroethane, and 6-amino-1-hexanol is 1g:(10~15)mL:(0.4~0.6)g.

[0028] Furthermore, in S1.2, the process conditions for the heating and reflux reaction are: temperature 78~82℃, time 6~8h.

[0029] In the above technical solution, in S1.1, under the action of the acid-binding agent 2,4,6-trimethylpyridine and at room temperature, one chlorine atom of cyanuric chloride undergoes a substitution reaction with the phenolic hydroxyl group of phenoxyethanol, retaining the remaining chlorine atom to obtain an antibacterial derivative; in S1.2, the primary amino group of 6-amino-1-hexanol is a strong nucleophilic group, which attacks the remaining chlorine atom, undergoing nucleophilic substitution, retaining the hydroxyl group to obtain a hydroxyl-terminated antibacterial derivative; In S1, the hydroxyl group of the hydroxyl-terminated antibacterial derivative reacts with the carboxyl group of 4-vinylbenzoic acid under the action of 4-dimethylaminopyridine to generate an ester bond and introduce a benzene ring, thus obtaining a double-bond-terminated ester compound; in S2, under the action of azobisisobutyronitrile, potassium propyl methacrylate and the double bond of the double-bond-terminated ester compound undergo free radical copolymerization, introducing the potassium sulfonate group, benzene ring, phenoxyethanol antibacterial group and triazine antibacterial group into the same compound, which is the antibacterial ester compound.

[0030] Compared with the prior art, the beneficial effects of the present invention are: 1. In this invention, a high-temperature resistant benzene ring is introduced into the molecular chain of the dispersant, which has better heat resistance than general polyether dispersants and is suitable for melt blending and extrusion with PET. In addition, the high-temperature resistant dispersant also has carboxyl groups and potassium sulfonate groups, which on the one hand have an adsorption effect on titanium nitride and enhance the dispersion performance of titanium nitride, and on the other hand, the introduction of potassium sulfonate groups makes the PET masterbatch obtained after blending and extrusion also have good antistatic properties, thereby improving the safety of PET masterbatch.

[0031] 2. In this invention, potassium sulfonate groups are also introduced into the antibacterial ester compounds, which endow PET with good ionic conductivity and can quickly release static electricity. Potassium sulfonate groups are strong polar groups and have good compatibility with PET. In addition, the titanium nitride slurry also contains potassium sulfonate groups, which can further enhance the compatibility of the ester bonds of the raw materials, thereby improving the overall performance of PET masterbatch. Furthermore, potassium sulfonate groups have high chemical bond energy, good thermal stability, and are not easily decomposed, which helps to reduce the probability of oxidative yellowing of PET masterbatch at high temperatures.

[0032] 3. In this invention, the phenoxyethanol antibacterial group and the triazine antibacterial group are fixed on the molecular chain of the antibacterial ester compound by chemical bonds. The two work synergistically to further improve the antibacterial properties of PET masterbatch. Moreover, the antibacterial ester compound has high-temperature resistant benzene rings and ester bonds, which is beneficial to improving the thermal decomposition temperature of the antibacterial group and its compatibility with PET. It is compatible with high-temperature processing environments and is conducive to achieving long-term antibacterial effects. Detailed Implementation

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] In the following examples, the relevant raw materials are: PET, grade RE19050; antioxidant 1010; titanium nitride powder with an average particle size of 20 nm and a specific surface area of ​​60.2 m². 2 / g; polyethylene glycol monoallyl ether, hydroxyl value 168~188 mgKOH / g; NaOH solution mass fraction 30%; the rest of the raw materials are commercially available.

[0035] Example 1 (1) Preparation of hydroxyl-terminated antibacterial derivatives: S1.1: Phenoxyethanol, cyanuric chloride, and dichloromethane were mixed and stirred to dissolve. 2,4,6-Trimethylpyridine was added, and the mixture was reacted at 26°C for 7 hours. After the reaction was completed, the mixture was extracted with deionized water and rotary evaporated at 35°C for 50 minutes to obtain the antibacterial derivative. S1.2: The antibacterial derivative and dichloroethane were mixed and stirred to dissolve. 6-Amino-1-hexanol was added, and the mixture was heated to 82°C and refluxed for 8 hours to obtain the hydroxyl-terminated antibacterial derivative. In S1.1, the ratio of phenoxyethanol, cyanuric chloride, dichloromethane, and 2,4,6-trimethylpyridine was 1 g: 0.9 g: 17 mL: 1.0 mL. In S1.2, the ratio of the antibacterial derivative, dichloroethane, and 6-amino-1-hexanol was 1 g: 15 mL: 0.6 g. (2) Preparation of antibacterial ester compounds: S1: A hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid, and 4-dimethylaminopyridine were mixed. Under a nitrogen atmosphere, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide were added and stirred until dissolved. The mixture was heated to 72°C and reacted for 12 hours to obtain a double-bond-terminated ester compound. S2: Potassium propyl 3-sulfonate methacrylate, the double-bond-terminated ester compound, azobisisobutyronitrile, and anhydrous ethanol were mixed in a ratio of 10g:30g:0.03g. Mix 800 mL of the mixture, heat to 70 °C, stir at 300 r / min for 4.0 h, after the reaction is complete, evaporate at 55 °C for 2.5 h, and dry at 60 °C for 8 h to obtain the antibacterial ester compound; in S1, the ratio of hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid, 4-dimethylaminopyridine, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide is 1 g: 0.7 g: 0.5 g: 4 mL: 2.4 mL; (3) Preparation of titanium nitride slurry: Step 1: Mix polyethylene glycol monoallyl ether and phthalic anhydride, heat to 100°C, then add 4-dimethylaminopyridine. Under nitrogen atmosphere, react at 100°C for 5 hours, then distill under reduced pressure at 0.095 MPa and 105°C for 2 hours to obtain a polyether ester containing double bonds. Step 2: Mix the polyether ester containing double bonds, potassium propyl 3-sulfonate methacrylate, sodium hypophosphite, and deionized water, heat to 75°C, then add methacrylic acid and ammonium persulfate. Under nitrogen atmosphere, react at 75°C for 4 hours. After the reaction, cool, and adjust the pH to 8 with NaOH solution to obtain a high-temperature resistant product. Dispersant; Step 3: Titanium nitride powder, high-temperature resistant dispersant and dipropylene glycol methyl ether acetate are mixed at a mass ratio of 20:6:75, and ball-milled at 550 r / min for 8 h with ZrO2 as the ball milling medium, and the ball-to-material ratio is 5:1 to obtain titanium nitride slurry; In Step 1, the mass ratio of polyethylene glycol monoallyl ether, phthalic anhydride and 4-dimethylaminopyridine is 10:0.9:0.20; In Step 2, the mass ratio of double-bonded polyether ester, potassium propyl methacrylate 3-sulfonate, sodium hypophosphite, deionized water, methacrylic acid and ammonium persulfate is 26:3.5:0.15:50:1.6:1.0; (4) Preparation of PET masterbatch modified with titanium nitride powder: PET, titanium nitride slurry, antibacterial ester compound, and antioxidant are mixed in a mass ratio of 75:25:18:4, melted, extruded, and granulated to obtain titanium nitride powder modified PET masterbatch.

[0036] Example 2 (1) Preparation of hydroxyl-terminated antibacterial derivatives: S1.1: Phenoxyethanol, cyanuric chloride, and dichloromethane were mixed and dissolved by stirring. 2,4,6-trimethylpyridine was added, and the mixture was reacted at 24°C for 6 hours. After the reaction was completed, the mixture was extracted with deionized water and rotary evaporated at 33°C for 40 minutes to obtain the antibacterial derivative. S1.2: The antibacterial derivative and dichloroethane were mixed and dissolved by stirring. 6-amino-1-hexanol was added, and the mixture was heated to 80°C and refluxed for 7 hours to obtain the hydroxyl-terminated antibacterial derivative. In S1.1, the ratio of phenoxyethanol, cyanuric chloride, dichloromethane, and 2,4,6-trimethylpyridine was 1 g: 0.8 g: 15 mL: 0.9 mL. In S1.2, the ratio of the antibacterial derivative, dichloroethane, and 6-amino-1-hexanol was 1 g: 13 mL: 0.5 g. (2) Preparation of antibacterial ester compounds: S1: A hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid, and 4-dimethylaminopyridine were mixed. Under a nitrogen atmosphere, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide were added and stirred until dissolved. The mixture was heated to 70°C and reacted for 11 hours to obtain a double-bond-terminated ester compound. S2: Potassium propyl 3-sulfonate methacrylate, the double-bond-terminated ester compound, azobisisobutyronitrile, and anhydrous ethanol were mixed in a ratio of 8g:25g:0.02g. Mix 650 mL of the mixture, heat to 68 °C, stir at 250 r / min for 3.8 h, after the reaction is complete, rotary evaporate at 50 °C for 2.0 h, and dry at 55 °C for 7 h to obtain the antibacterial ester compound; in S1, the ratio of hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid, 4-dimethylaminopyridine, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide is 1 g: 0.6 g: 0.4 g: 3 mL: 2.2 mL; (3) Preparation of titanium nitride slurry: Step 1: Mix polyethylene glycol monoallyl ether and phthalic anhydride, heat to 98°C, then add 4-dimethylaminopyridine. Under nitrogen atmosphere, react at 98°C for 4.5 h, then distill under reduced pressure at 0.090 MPa and 100°C for 1.8 h to obtain a polyether ester containing double bonds. Step 2: Mix the polyether ester containing double bonds, potassium propyl 3-sulfonate methacrylate, sodium hypophosphite, and deionized water, heat to 73°C, then add methacrylic acid and ammonium persulfate. Under nitrogen atmosphere, react at 73°C for 3 h. After the reaction, cool, and adjust the pH to 7 with NaOH solution to obtain a high-temperature resistant product. Dispersant; Step 3: Titanium nitride powder, high-temperature resistant dispersant and dipropylene glycol methyl ether acetate are mixed at a mass ratio of 20:5:70, and ball-milled at 500 r / min for 5 h with ZrO2 as the ball milling medium, and the ball-to-material ratio is 4:1 to obtain titanium nitride slurry; In Step 1, the mass ratio of polyethylene glycol monoallyl ether, phthalic anhydride and 4-dimethylaminopyridine is 9:0.8:0.15; In Step 2, the mass ratio of double-bonded polyether ester, potassium propyl methacrylate 3-sulfonate, sodium hypophosphite, deionized water, methacrylic acid and ammonium persulfate is 23:3.0:0.13:45:1.4:0.9; (4) Preparation of PET masterbatch modified with titanium nitride powder: PET, titanium nitride slurry, antibacterial ester compound, and antioxidant are mixed in a mass ratio of 65:20:14:3, melted, extruded, and granulated to obtain titanium nitride powder modified PET masterbatch.

[0037] Example 3 (1) Preparation of hydroxyl-terminated antibacterial derivatives: S1.1: Phenoxyethanol, cyanuric chloride, and dichloromethane were mixed and stirred to dissolve. 2,4,6-Trimethylpyridine was added, and the mixture was reacted at 22°C for 5 hours. After the reaction was completed, the mixture was extracted with deionized water and rotary evaporated at 30°C for 30 minutes to obtain the antibacterial derivative. S1.2: The antibacterial derivative and dichloroethane were mixed and stirred to dissolve. 6-Amino-1-hexanol was added, and the mixture was heated to 78°C and refluxed for 6 hours to obtain the hydroxyl-terminated antibacterial derivative. In S1.1, the ratio of phenoxyethanol, cyanuric chloride, dichloromethane, and 2,4,6-trimethylpyridine was 1 g: 0.7 g: 13 mL: 0.8 mL. In S1.2, the ratio of the antibacterial derivative, dichloroethane, and 6-amino-1-hexanol was 1 g: 10 mL: 0.4 g. (2) Preparation of antibacterial ester compounds: S1: A hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid, and 4-dimethylaminopyridine were mixed. Under a nitrogen atmosphere, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide were added and stirred until dissolved. The mixture was heated to 68°C and reacted for 10 hours to obtain a double-bond-terminated ester compound. S2: Potassium propyl 3-sulfonate methacrylate, the double-bond-terminated ester compound, azobisisobutyronitrile, and anhydrous ethanol were mixed in a ratio of 5g:20g:0.01g. Mix 500 mL of the mixture, heat to 65 °C, stir at 200 r / min for 3.5 h, after the reaction is complete, rotary evaporate at 45 °C for 1.5 h, and dry at 50 °C for 6 h to obtain the antibacterial ester compound; in S1, the ratio of hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid, 4-dimethylaminopyridine, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide is 1 g: 0.5 g: 0.3 g: 2 mL: 2.0 mL; (3) Preparation of titanium nitride slurry: Step 1: Mix polyethylene glycol monoallyl ether and phthalic anhydride, heat to 95°C, then add 4-dimethylaminopyridine. Under nitrogen atmosphere, maintain the reaction at 95°C for 4 hours, then distill under reduced pressure at 0.085 MPa and 95°C for 1.5 hours to obtain a polyether ester containing double bonds. Step 2: Mix the polyether ester containing double bonds, potassium propyl 3-sulfonate methacrylate, sodium hypophosphite, and deionized water, heat to 70°C, then add methacrylic acid and ammonium persulfate. Under nitrogen atmosphere, maintain the reaction at 70°C for 2 hours. After the reaction, cool, and adjust the pH to 6 with NaOH solution to obtain a high-temperature resistant product. Dispersant; Step 3: Mix titanium nitride powder, high-temperature resistant dispersant and dipropylene glycol methyl ether acetate at a mass ratio of 20:4:65, use ZrO2 as the ball milling medium, and ball mill at 450 r / min for 3 h, with a ball-to-material ratio of 3:1 to obtain titanium nitride slurry; In Step 1, the mass ratio of polyethylene glycol monoallyl ether, phthalic anhydride, and 4-dimethylaminopyridine is 8:0.7:0.10; In Step 2, the mass ratio of double-bonded polyether ester, potassium propyl methacrylate 3-sulfonate, sodium hypophosphite, deionized water, methacrylic acid, and ammonium persulfate is 20:2.5:0.10:40:1.2:0.8; (4) Preparation of PET masterbatch modified with titanium nitride powder: PET, titanium nitride slurry, antibacterial ester compound, and antioxidant are mixed in a mass ratio of 55:15:10:2, melted, extruded, and granulated to obtain titanium nitride powder modified PET masterbatch.

[0038] Comparative Example 1: Unlike Example 1, titanium nitride powder was mixed with PET, antibacterial ester compound, and antioxidant, while the remaining steps remained the same as in Example 1; the specific process is as follows: (1) Preparation of hydroxyl-terminated antibacterial derivatives: S1.1: Phenoxyethanol, cyanuric chloride, and dichloromethane were mixed and stirred to dissolve. 2,4,6-Trimethylpyridine was added, and the mixture was reacted at 26°C for 7 hours. After the reaction was completed, the mixture was extracted with deionized water and rotary evaporated at 35°C for 50 minutes to obtain the antibacterial derivative. S1.2: The antibacterial derivative and dichloroethane were mixed and stirred to dissolve. 6-Amino-1-hexanol was added, and the mixture was heated to 82°C and refluxed for 8 hours to obtain the hydroxyl-terminated antibacterial derivative. In S1.1, the ratio of phenoxyethanol, cyanuric chloride, dichloromethane, and 2,4,6-trimethylpyridine was 1 g: 0.9 g: 17 mL: 1.0 mL. In S1.2, the ratio of the antibacterial derivative, dichloroethane, and 6-amino-1-hexanol was 1 g: 15 mL: 0.6 g. (2) Preparation of antibacterial ester compounds: S1: A hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid, and 4-dimethylaminopyridine were mixed. Under a nitrogen atmosphere, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide were added and stirred until dissolved. The mixture was heated to 72°C and reacted for 12 hours to obtain a double-bond-terminated ester compound. S2: Potassium propyl 3-sulfonate methacrylate, the double-bond-terminated ester compound, azobisisobutyronitrile, and anhydrous ethanol were mixed in a ratio of 10g:30g:0.03g. Mix 800 mL of the mixture, heat to 70 °C, stir at 300 r / min for 4.0 h, after the reaction is complete, evaporate at 55 °C for 2.5 h, and dry at 60 °C for 8 h to obtain the antibacterial ester compound; in S1, the ratio of hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid, 4-dimethylaminopyridine, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide is 1 g: 0.7 g: 0.5 g: 4 mL: 2.4 mL; (3) Preparation of PET masterbatch modified with titanium nitride powder: PET, titanium nitride powder, antibacterial ester compound, and antioxidant are mixed in a mass ratio of 75:5:18:4, melted, extruded, and granulated to obtain titanium nitride powder modified PET masterbatch.

[0039] Comparative Example 2: Unlike Example 1, the hydroxyl-terminated antibacterial derivative was replaced with ethylene glycol, which does not have antibacterial properties. The remaining steps remained the same as in Example 1. The specific process is as follows: (1) Preparation of ester compounds: S1: Ethylene glycol, 4-vinylbenzoic acid, and 4-dimethylaminopyridine were mixed and dissolved under a nitrogen atmosphere by adding N,N-dimethylformamide and N,N'-diisopropylcarbodiimide. The mixture was then heated to 72°C and reacted for 12 hours to obtain a double-bond-terminated ester compound. S2: Potassium propyl 3-sulfonate methacrylate, the double-bond-terminated ester compound, azobisisobutyronitrile, and anhydrous ethanol were mixed in a ratio of 10g:30g:0.03g. Mix 800 mL of the mixture, heat to 70 °C, stir at 300 r / min for 4.0 h, after the reaction is complete, rotary evaporate at 55 °C for 2.5 h, and dry at 60 °C for 8 h to obtain the antibacterial ester compound; in S1, the ratio of ethylene glycol, 4-vinylbenzoic acid, 4-dimethylaminopyridine, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide is 1 g: 0.7 g: 0.5 g: 4 mL: 2.4 mL; (2) Preparation of titanium nitride slurry: Step 1: Mix polyethylene glycol monoallyl ether and phthalic anhydride, heat to 100°C, then add 4-dimethylaminopyridine. Under nitrogen atmosphere, react at 100°C for 5 hours, then distill under reduced pressure at 0.095 MPa and 105°C for 2 hours to obtain a polyether ester containing double bonds. Step 2: Mix the polyether ester containing double bonds, potassium propyl 3-sulfonate methacrylate, sodium hypophosphite, and deionized water, heat to 75°C, then add methacrylic acid and ammonium persulfate. Under nitrogen atmosphere, react at 75°C for 4 hours. After the reaction, cool, and adjust the pH to 8 with NaOH solution to obtain a high-temperature resistant product. Dispersant; Step 3: Titanium nitride powder, high-temperature resistant dispersant and dipropylene glycol methyl ether acetate are mixed at a mass ratio of 20:6:75, and ball-milled at 550 r / min for 8 h with ZrO2 as the ball milling medium, and the ball-to-material ratio is 5:1 to obtain titanium nitride slurry; In Step 1, the mass ratio of polyethylene glycol monoallyl ether, phthalic anhydride and 4-dimethylaminopyridine is 10:0.9:0.20; In Step 2, the mass ratio of double-bonded polyether ester, potassium propyl methacrylate 3-sulfonate, sodium hypophosphite, deionized water, methacrylic acid and ammonium persulfate is 26:3.5:0.15:50:1.6:1.0; (3) Preparation of PET masterbatch modified with titanium nitride powder: PET, titanium nitride slurry, ester compounds, and antioxidants are mixed in a mass ratio of 75:25:18:4, melted, extruded, and granulated to obtain titanium nitride powder modified PET masterbatch.

[0040] Comparative Example 3: Unlike Example 1, the double-bond-terminated ester compound was directly blended with PET, titanium nitride slurry, and antioxidant. The remaining steps were unchanged and were the same as in Example 1. The specific process is as follows: (1) Preparation of double-bond-terminated ester compounds: S1.1: Phenoxyethanol, cyanuric chloride, and dichloromethane were mixed and dissolved by stirring. 2,4,6-Trimethylpyridine was added, and the mixture was reacted at 26°C for 7 hours. After the reaction, the mixture was extracted with deionized water and rotary evaporated at 35°C for 50 minutes to obtain the antibacterial derivative. S1.2: The antibacterial derivative and dichloroethane were mixed and dissolved by stirring. 6-Amino-1-hexanol was added, and the mixture was heated to 82°C and refluxed for 8 hours to obtain the hydroxyl-terminated antibacterial derivative. S1.3: The hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid, and 4-dimethylaminopyridine were mixed. Under a nitrogen atmosphere, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide were added and dissolved by stirring. The mixture was heated to 72°C and reacted for 12 hours to obtain a double-bond-terminated ester compound. In S1, the hydroxyl-terminated antibacterial derivative… In S1.1, the ratio of antibacterial derivative, 4-vinylbenzoic acid, 4-dimethylaminopyridine, N,N-dimethylformamide, and N,N'-diisopropylcarbodiimide is 1g:0.7g:0.5g:4mL:2.4mL; in S1.2, the ratio of antibacterial derivative, dichloroethane, and 2,4,6-trimethylpyridine is 1g:0.9g:17mL:1.0mL; in S1.3, the ratio of antibacterial derivative, 4-vinylbenzoic acid, 4-dimethylaminopyridine, N,N-dimethylformamide, and N,N'-diisopropylcarbodiimide is 1g:0.7g:0.5g:4mL:2.4mL. (2) Preparation of titanium nitride slurry: Step 1: Mix polyethylene glycol monoallyl ether and phthalic anhydride, heat to 100°C, then add 4-dimethylaminopyridine. Under nitrogen atmosphere, react at 100°C for 5 hours, then distill under reduced pressure at 0.095 MPa and 105°C for 2 hours to obtain a polyether ester containing double bonds. Step 2: Mix the polyether ester containing double bonds, potassium propyl 3-sulfonate methacrylate, sodium hypophosphite, and deionized water, heat to 75°C, then add methacrylic acid and ammonium persulfate. Under nitrogen atmosphere, react at 75°C for 4 hours. After the reaction, cool, and adjust the pH to 8 with NaOH solution to obtain a high-temperature resistant product. Dispersant; Step 3: Titanium nitride powder, high-temperature resistant dispersant and dipropylene glycol methyl ether acetate are mixed at a mass ratio of 20:6:75, and ball-milled at 550 r / min for 8 h with ZrO2 as the ball milling medium, and the ball-to-material ratio is 5:1 to obtain titanium nitride slurry; In Step 1, the mass ratio of polyethylene glycol monoallyl ether, phthalic anhydride and 4-dimethylaminopyridine is 10:0.9:0.20; In Step 2, the mass ratio of double-bonded polyether ester, potassium propyl methacrylate 3-sulfonate, sodium hypophosphite, deionized water, methacrylic acid and ammonium persulfate is 26:3.5:0.15:50:1.6:1.0; (3) Preparation of PET masterbatch modified with titanium nitride powder: PET, titanium nitride slurry, double bond-terminated ester compound, and antioxidant were mixed in a mass ratio of 75:25:18:4, melted, extruded, and granulated to obtain titanium nitride powder modified PET masterbatch.

[0041] Comparative Example 4: Unlike Example 1, titanium nitride powder was mixed with PET and an antioxidant. The remaining steps were unchanged and were the same as in Example 1. The specific process is as follows: PET, titanium nitride powder, and antioxidant are mixed in a mass ratio of 75:5:4, melted, extruded, and granulated to obtain titanium nitride powder modified PET masterbatch.

[0042] experiment: Antistatic properties: The surface resistance of the titanium nitride powder modified PET masterbatch was tested according to GB / T 31838.2-2019 to characterize its antistatic properties. Antibacterial test: The antibacterial rate of the prepared titanium nitride powder modified PET masterbatch was tested in accordance with GB / T 31402-2023 to characterize its antibacterial properties; The experimental data are shown in Table 1 below;

[0043] Based on the information in the table above, the following conclusions can be drawn: Compared with Example 1, Comparative Example 1 replaced titanium nitride slurry with titanium nitride powder, and the surface resistivity of the modified PET masterbatch increased significantly. Compared with Example 1, Comparative Example 2 replaced the hydroxyl-capped antibacterial derivative with ethylene glycol, which does not have antibacterial properties, and the antibacterial rate of the modified PET masterbatch was significantly reduced. Compared with Example 1, Comparative Example 3 directly blended double-bond-terminated ester compounds with PET, titanium nitride slurry, and antioxidants, resulting in increased surface resistance and decreased antibacterial rate of the modified PET masterbatch. Compared with Example 1, Comparative Example 4 replaced titanium nitride slurry with titanium nitride powder and did not add antibacterial ester compounds. The surface resistance of the modified PET masterbatch increased and the antibacterial rate decreased significantly. As can be seen from the above, the preparation of antibacterial ester compounds and titanium nitride slurry in this application can promote the comprehensive improvement of the antistatic and antibacterial properties of the titanium nitride powder modified PET masterbatch.

[0044] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A method for preparing titanium nitride powder modified PET masterbatch, characterized in that: Including the following processes: PET, titanium nitride slurry, antibacterial ester compound, and antioxidant are mixed, melted, extruded, and granulated to obtain titanium nitride powder modified PET masterbatch; The titanium nitride slurry includes titanium nitride powder, a high-temperature resistant dispersant, and dipropylene glycol methyl ether acetate. The antibacterial ester compounds include phenoxyethanol antibacterial groups and triazine antibacterial groups.

2. The method for preparing titanium nitride powder modified PET masterbatch according to claim 1, characterized in that: The preparation process of the titanium nitride slurry is as follows: Step 1: Mix polyethylene glycol monoallyl ether and phthalic anhydride, heat to 95~100℃, add 4-dimethylaminopyridine, keep the reaction under nitrogen atmosphere, and distill under reduced pressure to obtain polyether ester containing double bonds. Step 2: Mix the double-bonded polyether ester, potassium propyl 3-sulfonate methacrylate, sodium hypophosphite, and deionized water, heat to 70-75°C, then add methacrylic acid and ammonium persulfate, and keep the reaction under nitrogen atmosphere. After the reaction is complete, cool and adjust the pH to 6-8 with NaOH solution to obtain a high-temperature resistant dispersant. Step 3: Mix titanium nitride powder, high-temperature resistant dispersant and dipropylene glycol methyl ether acetate, and ball mill to obtain titanium nitride slurry.

3. The method for preparing titanium nitride powder modified PET masterbatch according to claim 1, characterized in that: The preparation process of the antibacterial ester compound is as follows: S1: A hydroxyl-terminated antibacterial derivative, 4-vinylbenzoic acid and 4-dimethylaminopyridine were mixed, and N,N-dimethylformamide and N,N'-diisopropylcarbodiimide were added under a nitrogen atmosphere and stirred to dissolve. The mixture was then heated to react and a double-bond-terminated ester compound was obtained. S2: Potassium propyl 3-sulfonate methacrylate, double-bond-terminated ester compounds, azobisisobutyronitrile, and anhydrous ethanol are mixed, heated, stirred, and reacted. After the reaction is completed, the mixture is rotary evaporated and dried to obtain antibacterial ester compounds.

4. The method for preparing titanium nitride powder modified PET masterbatch according to claim 3, characterized in that: The hydroxyl-terminated antibacterial derivative is prepared by the following process: S1.1: Phenoxyethanol, cyanuric chloride and dichloromethane are mixed and stirred to dissolve. 2,4,6-trimethylpyridine is added and reacted at room temperature. After the reaction is completed, the mixture is extracted with deionized water and rotary evaporated to obtain the antibacterial derivative. S1.2: Mix the antibacterial derivative and dichloroethane, stir to dissolve, add 6-amino-1-hexanol, and heat under reflux to obtain the hydroxyl-terminated antibacterial derivative.

5. The method for preparing titanium nitride powder modified PET masterbatch according to claim 2, characterized in that: In step 1, the mass ratio of polyethylene glycol monoallyl ether, phthalic anhydride, and 4-dimethylaminopyridine is (8~10):(0.7~0.9):(0.10~0.20).

6. The method for preparing titanium nitride powder modified PET masterbatch according to claim 2, characterized in that: In step 2, the mass ratio of double-bonded polyether ester, potassium propyl 3-sulfonate methacrylate, sodium hypophosphite, deionized water, methacrylic acid and ammonium persulfate is (20~26): (2.5~3.5): (0.10~0.15): (40~50): (1.2~1.6): (0.8~1.0).

7. The method for preparing titanium nitride powder modified PET masterbatch according to claim 2, characterized in that: In step 3, the mass ratio of titanium nitride powder, high-temperature resistant dispersant and dipropylene glycol methyl ether acetate is 20:(4~6):(65~75).

8. The method for preparing titanium nitride powder modified PET masterbatch according to claim 3, characterized in that: In S1, the ratio of hydroxyl-capped antibacterial derivative, 4-vinylbenzoic acid, 4-dimethylaminopyridine, N,N-dimethylformamide and N,N'-diisopropylcarbodiimide is 1 g : (0.5~0.7) g : (0.3~0.5) g : (2~4) mL : (2.0~2.4) mL.

9. The method for preparing titanium nitride powder modified PET masterbatch according to claim 1, characterized in that: The mass ratio of PET, titanium nitride slurry, antibacterial ester compound and antioxidant is (55~75): (15~25): (10~18): (2~4).

10. The titanium nitride powder modified PET masterbatch prepared by the method of preparing titanium nitride powder modified PET masterbatch according to any one of claims 1 to 9.

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