A high-elastic antibacterial PETG material, preparation method and medical packaging material

Abstract

The present invention relates to the technical field of polymer materials, specifically a kind of high elastic antibacterial PETG material, preparation method and medical packaging material. The preparation method comprises the following steps: using graphene oxide to load nano silver particles, obtain an antibacterial agent, then modifying the surface of the antibacterial agent with 3-aminopropyl triethoxysilane, obtain a modified antibacterial agent, reacting diisocyanate, polyester polyol, and hydroxyl-terminated polysiloxane, then adding modified antibacterial agent, amoxicillin, chain extender, catalyst, stirring reaction, obtain modified polyurethane loaded antibacterial agent, modified polyurethane loaded antibacterial agent, dibutyltin dilaurate, PETG melt blending, extrusion tableting, obtain high elastic antibacterial PETG material. The high elastic antibacterial PETG material of the present invention has high elasticity and excellent antibacterial performance, and can be used in packaging fields such as medical packaging.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a high-elasticity antibacterial PETG material, a preparation method and a medical packaging material. Background Art

[0002] PETG material is a new type of polyester material, which is obtained by condensation polymerization of three monomers: terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol. It has good viscosity, transparency, color, chemical stability, and thermoforming properties, but its toughness is relatively poor, which has certain limitations on its application range.

[0003] Chinese patent CN112266584B discloses a high-cushioning PETG material and its application, wherein PETG resin, polyolefin elastomer, natural rubber, polyvinyl chloride, heat stabilizer, and compatibilizer are uniformly mixed, melt blended, and extruded to obtain a high-cushioning PETG material. However, the tensile strength of the high-cushioning PETG material is only 38.5MPa at most, which still needs to be improved; Chinese patent CN112812521B discloses a PETG antibacterial composite film and its preparation method, wherein the Ag / TiO2 composite antibacterial agent is prepared by sol-gel method, polylactic acid is used as carrier resin, ultrasonic mixing, melt spinning, and further melt extruded with PETG as antibacterial agent masterbatch to obtain a PETG antibacterial composite film, but the Ag / TiO2 composite antibacterial agent is an inorganic powder, and although polylactic acid is used as carrier resin to be dispersed in the matrix resin, it is not linked by chemical bonds, and is easily precipitated from the matrix material over time, affecting the performance of the material. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a method for preparing a high-elasticity antibacterial PETG material, which solves the problem that the PETG material has poor elasticity and insufficiently durable antibacterial performance.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a highly elastic antibacterial PETG material comprises the following steps:

[0007] Step (1), mixing graphene oxide, silver nitrate and water, ultrasonically dispersing, adding ascorbic acid, continuing ultrasonic dispersion, heating to react, filtering, washing and drying after the reaction to obtain an antibacterial agent;

[0008] Step (2), mixing the antibacterial agent, 3-aminopropyltriethoxysilane and ethanol aqueous solution, ultrasonically dispersing, heating to react, and after the reaction, continuing to heat to react, cooling to room temperature, filtering, washing and drying to obtain a modified antibacterial agent;

[0009] Step (3), uniformly mixing the modified antibacterial agent, amoxicillin, ethylenediamine and acetone, and ultrasonically dispersing the mixture to obtain an antibacterial component dispersion;

[0010] The diisocyanate, polyester polyol and hydroxyl-terminated polysiloxane are mixed uniformly, stirred and heated to a first set temperature, reacted, cooled to a second reaction temperature, a chain extender and a catalyst are added, reacted, cooled to a third reaction temperature, an antibacterial component dispersion is added, reacted, and after the reaction is completed, precipitated, filtered, and dried to obtain a modified polyurethane-loaded antibacterial agent;

[0011] Step (4), melt-blending the modified polyurethane loaded antibacterial agent, dibutyltin dilaurate and PETG, and extruding and tableting to obtain a high-elastic antibacterial PETG material.

[0012] Preferably, in the step (1), the mass ratio of graphene oxide, silver nitrate, water and ascorbic acid is (3-7):(1.3-2.6):750:(32-40), the temperature reaction condition is: react at 90-100°C for 18-20h; the ultrasonic dispersion condition is: ultrasonic at a frequency of 20-40kHz for 20-40min, the condition for continued ultrasonic dispersion is: ultrasonic at a frequency of 20-40kHz for 50-70min, and the drying condition is: drying at 80-100°C for 1-2h under a nitrogen atmosphere.

[0013] Preferably, in step (2), the mass ratio of ethanol to water in the ethanol aqueous solution is 5:95; the mass ratio of the antibacterial agent, 3-aminopropyltriethoxysilane, and the ethanol aqueous solution is (1-3):1:100.

[0014] Preferably, in step (2), the conditions for ultrasonic dispersion are: ultrasonication at a frequency of 20-40 kHz for 20-40 min, the conditions for temperature increase reaction are: reaction at a temperature of 45-55°C for 75-105 min, the conditions for continued temperature increase reaction are: reaction at a temperature of 65-75°C for 50-70 min, and the conditions for drying are: drying at 80-100°C for 1-2 h under a nitrogen atmosphere.

[0015] Preferably, in step (3): the mass ratio of the antibacterial component dispersion, diisocyanate, polyester polyol, hydroxyl-terminated polysiloxane, chain extender, and catalyst is: (50-65):(220-250):(160-400):(300-600):(35-65):(7-11); in the antibacterial component dispersion, the mass ratio of the modified antibacterial agent, amoxicillin, ethylenediamine, and acetone is: (3-7):(4-6):0.6:40. Preferably, in step (3), the diisocyanate is at least one of diphenylmethane diisocyanate and isophorone diisocyanate, the polyester polyol is polycaprolactone diol with a relative molecular weight of 400-1000, the hydroxyl-terminated polysiloxane is hydroxyalkyl silicone oil with a relative molecular weight of 2000-3000, the chain extender is at least one of 1,4-butanediol and 2,2-dihydroxymethylbutyric acid, and the catalyst is dibutyltin dilaurate.

[0016] Preferably, in step (3), the first set temperature is 85-95°C, the reaction time is 2-3h, the second set temperature is 75-85°C, the reaction time is 1.5-2.5h, the third set temperature is 50°C, the reaction time is 0.5h, the precipitation agent is deionized water, and the drying conditions are: drying at 70-90°C for 4-6h,

[0017] Preferably, in step (4), the mass ratio of the modified polyurethane loaded antibacterial agent, dibutyltin dilaurate, and PETG is: (25-30):0.5:(70-75); the temperature of melt blending is: 260-280° C., and the blending time is 20-30 min.

[0018] Preferably, a high elasticity antibacterial PETG material is prepared by the above-mentioned method for preparing the high elasticity antibacterial PETG material.

[0019] An application of the above-mentioned high elasticity antibacterial PETG material in medical packaging, the application includes a medical packaging material prepared based on the high elasticity antibacterial PETG material.

[0020] Preferably, the packaging material comprises a packaging bag or a packaging film.

[0021] Preferably, the method for preparing the packaging film comprises the following steps:

[0022] The high-elastic antibacterial PETG material is preheated, stretched, trimmed, and rolled to obtain the high-elastic antibacterial PETG film material;

[0023] The preheating temperature is 90°C and the stretching ratio is 3.5-4.5 times.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1. The present invention firstly loads nano-silver particles with graphene oxide to obtain an antibacterial agent. On the one hand, graphene oxide has good antibacterial ability, and nano-silver particles can generate silver ions to play an antibacterial role. The two are used in combination to effectively improve the antibacterial performance. On the other hand, the use of graphene oxide to load nano-silver can effectively prevent the nano-silver from being rapidly oxidized into silver ions, thereby prolonging the antibacterial time. Then, 3-aminopropyltriethoxysilane is used to modify the surface of the antibacterial agent, and amino groups are introduced on the surface of the antibacterial agent. The amino groups react with isocyanate groups and are loaded on modified polyurethane, thereby increasing the compatibility of the antibacterial agent with a matrix material.

[0026] 2. Amoxicillin and polysiloxane segments are introduced into polyurethane. Amoxicillin not only has excellent antibacterial properties, but also forms a synergistic effect with antibacterial agents to further improve the antibacterial properties of the material. It can also form chelates with oxidized silver ions to achieve a sustained release effect, further extending the antibacterial time. The polysiloxane segments introduced into polyurethane increase the hydrophobicity of the material, preventing polyester hydrolysis caused by water absorption and material performance degradation caused by silver ion loss. At the same time, polyurethane has excellent flexibility and elasticity. There are polyester polyol segments in its segments, which can undergo an ester exchange reaction with PETG under the catalysis of dibutyltin dilaurate, so that the PETG segments are directly connected to the polyurethane segments, which can effectively increase the elasticity and elongation at break of PETG. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a process flow chart of the preparation of the high elastic antibacterial PETG material of the present invention;

[0028] Figure 2 It is a bar chart of the test results of the tensile strength of the high elastic antibacterial PETG materials prepared in Examples 1-5 of the present invention and Comparative Examples 1-3;

[0029] Figure 3 It is a bar graph of the test results of the elongation at break of the high elastic antibacterial PETG materials prepared in Examples 1-5 of the present invention and Comparative Examples 1-3;

[0030] Figure 4 It is a bar chart of the test results of the tensile elastic modulus of the high elastic antibacterial PETG materials prepared in Examples 1-5 of the present invention and Comparative Examples 1-3;

[0031] Figure 5 It is a bar chart of the test results of the antibacterial effect of the high elastic antibacterial PETG materials prepared in Examples 1-5 of the present invention and Comparative Examples 1-3 before and after being placed at 50° C. and 80% humidity for 50 days. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than 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 work are within the scope of protection of the present invention.

[0033] Example 1

[0034] This embodiment discloses a method for preparing a highly elastic antibacterial PETG material, comprising the following steps:

[0035] (1) Graphene oxide, silver nitrate and water are mixed uniformly, ultrasonicated at a frequency of 20 kHz for 40 minutes, ascorbic acid is added, ultrasonicated at a frequency of 20 kHz for 70 minutes, the temperature is raised to 90° C., and the temperature is kept for reaction for 20 hours. After the reaction is completed, the mixture is filtered, washed with deionized water, and dried at 80° C. for 2 hours under a nitrogen atmosphere to obtain an antibacterial agent;

[0036] Among them, the mass ratio of graphene oxide, silver nitrate, water and ascorbic acid is 3:1.3:750:32.

[0037] (2) The antibacterial agent, 3-aminopropyltriethoxysilane, and ethanol aqueous solution were mixed uniformly in a mass ratio of 1:1:100, ultrasonicated at a frequency of 20 kHz for 40 minutes, heated to 45°C for reaction for 105 minutes, and then heated to 65°C for reaction for 70 minutes. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with water, and dried at 80°C for 2 hours under a nitrogen atmosphere to obtain a modified antibacterial agent;

[0038] Wherein, the mass ratio of ethanol to water in the ethanol aqueous solution is 5:95;

[0039] (3) The modified antibacterial agent, amoxicillin, ethylenediamine, and acetone were uniformly mixed in a mass ratio of 3:4:0.6:40, and ultrasonicated at a frequency of 20 kHz for 40 minutes to obtain an antibacterial component dispersion;

[0040] (4) Diphenylmethane diisocyanate, polycaprolactone (relative molecular weight of 400), and hydroxyl silicone oil (relative molecular weight of 2000) were mixed evenly, stirred and heated to 85°C, reacted for 3 hours, cooled to 75°C after the reaction, added 1,4-butanediol and dibutyltin dilaurate, reacted for 2.5 hours, cooled to 50°C after the reaction, added antibacterial component dispersion, reacted for 0.5 hours, added deionized water until the solid precipitate no longer increased, filtered, and dried at 70°C for 6 hours to obtain a modified polyurethane-loaded antibacterial agent;

[0041] The mass ratio of the antibacterial component dispersion, diphenylmethane diisocyanate, polycaprolactone, hydroxyalkyl silicone oil, 1,4-butanediol, and dibutyltin dilaurate is 50:220:160:300:35:7;

[0042] (5) The modified polyurethane loaded antibacterial agent, dibutyltin dilaurate, and PETG were uniformly mixed in a mass ratio of 25:0.5:75, melt-blended at 260° C. for 30 min, and extruded and sheeted to obtain a highly elastic antibacterial PETG material.

[0043] Example 2

[0044] This embodiment discloses a method for preparing a highly elastic antibacterial PETG material, comprising the following steps:

[0045] (1) Graphene oxide, silver nitrate and water are mixed uniformly, ultrasonicated at a frequency of 30 kHz for 30 minutes, ascorbic acid is added, ultrasonicated at a frequency of 30 kHz for 60 minutes, the temperature is raised to 95° C., and the temperature is kept for reaction for 19 hours. After the reaction is completed, the mixture is filtered, washed with deionized water, and dried at 90° C. for 1.5 hours under a nitrogen atmosphere to obtain an antibacterial agent;

[0046] Among them, the mass ratio of graphene oxide, silver nitrate, water and ascorbic acid is 4:2.0:750:35.

[0047] (2) The antibacterial agent, 3-aminopropyltriethoxysilane, and ethanol aqueous solution were mixed uniformly in a mass ratio of 1.5:1:100, ultrasonicated at a frequency of 30 kHz for 30 min, heated to 50 ° C for reaction for 90 min, and continued to heat to 70 ° C for reaction for 60 min. After the reaction was completed, it was cooled to room temperature, filtered, washed with water, and dried at 90 ° C for 1.5 h under a nitrogen atmosphere to obtain a modified antibacterial agent;

[0048] Wherein, the mass ratio of ethanol to water in the ethanol aqueous solution is 5:95;

[0049] (3) The modified antibacterial agent, amoxicillin, ethylenediamine, and acetone were uniformly mixed in a mass ratio of 4:5:0.6:40, and ultrasonicated at a frequency of 30 kHz for 30 min to obtain an antibacterial component dispersion;

[0050] (4) Diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone (relative molecular weight of 530), and hydroxyl silicone oil (relative molecular weight of 2000) were mixed evenly, stirred and heated to 90°C, reacted for 2.5 hours, cooled to 80°C after the reaction, added 1,4-butanediol and dibutyltin dilaurate, reacted for 2 hours, cooled to 50°C after the reaction, added antibacterial component dispersion, reacted for 0.5 hours, added deionized water until the solid precipitate no longer increased, filtered, and dried at 80°C for 5 hours to obtain a modified polyurethane-loaded antibacterial agent;

[0051] The mass ratio of the antibacterial component dispersion, diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone, hydroxyalkyl silicone oil, 1,4-butanediol, and dibutyltin dilaurate is 50:110:120:220:400:45:8;

[0052] (5) The modified polyurethane loaded antibacterial agent, dibutyltin dilaurate, and PETG were uniformly mixed in a mass ratio of 26:0.5:74, melt-blended at 270°C for 25 minutes, and extruded and sheeted to obtain a highly elastic antibacterial PETG material.

[0053] Example 3

[0054] This embodiment discloses a method for preparing a highly elastic antibacterial PETG material, comprising the following steps:

[0055] (1) Graphene oxide, silver nitrate and water are mixed uniformly, ultrasonicated at a frequency of 30 kHz for 30 minutes, ascorbic acid is added, ultrasonicated at a frequency of 30 kHz for 60 minutes, the temperature is raised to 95° C., and the temperature is kept for reaction for 19 hours. After the reaction is completed, the mixture is filtered, washed with deionized water, and dried at 90° C. for 1.5 hours under a nitrogen atmosphere to obtain an antibacterial agent;

[0056] Among them, the mass ratio of graphene oxide, silver nitrate, water, and ascorbic acid is 5:2.0:750:35;

[0057] (2) The antibacterial agent, 3-aminopropyltriethoxysilane, and ethanol aqueous solution were mixed uniformly in a mass ratio of 2:1:100, ultrasonicated at a frequency of 30 kHz for 30 min, heated to 50 ° C for reaction for 90 min, and then heated to 70 ° C for reaction for 60 min. After the reaction, the mixture was cooled to room temperature, filtered, washed with water, and dried at 90 ° C for 1.5 h under a nitrogen atmosphere to obtain a modified antibacterial agent;

[0058] Wherein, the mass ratio of ethanol to water in the ethanol aqueous solution is 5:95;

[0059] (3) The modified antibacterial agent, amoxicillin, ethylenediamine, and acetone were uniformly mixed in a mass ratio of 4:5:0.6:40, and ultrasonicated at a frequency of 30 kHz for 30 min to obtain an antibacterial component dispersion;

[0060] (4) Diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone (relative molecular weight of 800), and hydroxyl silicone oil (relative molecular weight of 2000) were mixed evenly, stirred and heated to 90°C, reacted for 2.5 hours, cooled to 80°C after the reaction, added 1,4-butanediol and dibutyltin dilaurate, reacted for 2 hours, cooled to 50°C after the reaction, added antibacterial component dispersion, reacted for 0.5 hours, added deionized water until the solid precipitate no longer increased, filtered, and dried at 80°C for 5 hours to obtain a modified polyurethane-loaded antibacterial agent;

[0061] The mass ratio of the antibacterial component dispersion, diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone, hydroxyalkyl silicone oil, 1,4-butanediol, and dibutyltin dilaurate is 55:120:120:280:400:45:9.

[0062] (5) The modified polyurethane loaded antibacterial agent, dibutyltin dilaurate, and PETG were uniformly mixed in a mass ratio of 27.5:0.5:72.5, melt-blended at 270° C. for 25 min, and extruded and sheeted to obtain a highly elastic antibacterial PETG material.

[0063] Example 4

[0064] This embodiment discloses a method for preparing a highly elastic antibacterial PETG material, comprising the following steps:

[0065] (1) Graphene oxide, silver nitrate and water are mixed uniformly, ultrasonicated at a frequency of 30 kHz for 30 min, ascorbic acid is added, ultrasonicated at a frequency of 30 kHz for 60 min, the temperature is raised to 95° C., and the reaction is kept warm for 19 h. After the reaction is completed, the mixture is filtered, washed with deionized water, and dried at 90° C. for 1.5 h under a nitrogen atmosphere to obtain an antibacterial agent;

[0066] Among them, the mass ratio of graphene oxide, silver nitrate, water, and ascorbic acid is 6:2.0:750:35;

[0067] (2) The antibacterial agent, 3-aminopropyltriethoxysilane, and ethanol aqueous solution were mixed uniformly in a mass ratio of 2.5:1:100, ultrasonicated at a frequency of 30 kHz for 30 min, heated to 50° C. for reaction for 90 min, and then heated to 70° C. for reaction for 60 min. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with water, and dried at 90° C. for 1.5 h under a nitrogen atmosphere to obtain a modified antibacterial agent;

[0068] Wherein, the mass ratio of ethanol to water in the ethanol aqueous solution is 5:95;

[0069] (3) The modified antibacterial agent, amoxicillin, ethylenediamine, and acetone were uniformly mixed in a mass ratio of 6:5:0.6:40, and ultrasonicated at a frequency of 30 kHz for 30 min to obtain an antibacterial component dispersion;

[0070] (4) Diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone (relative molecular weight of 800), and hydroxyl silicone oil (relative molecular weight of 3000) were mixed evenly, stirred and heated to 90°C, reacted for 2.5 hours, cooled to 80°C after the reaction, added 1,4-butanediol, 2,2-dihydroxymethylbutyric acid, and dibutyltin dilaurate, reacted for 2 hours, cooled to 50°C after the reaction, added antibacterial component dispersion, reacted for 0.5 hours, added deionized water until the solid precipitate no longer increased, filtered, and dried at 80°C for 5 hours to obtain a modified polyurethane-loaded antibacterial agent;

[0071] The mass ratio of the antibacterial component dispersion, diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone, hydroxyalkyl silicone oil, 1,4-butanediol, 2,2-dihydroxymethylbutyric acid, and dibutyltin dilaurate is 60:120:120:340:500:30:25:10;

[0072] (5) The modified polyurethane loaded antibacterial agent, dibutyltin dilaurate, and PETG were uniformly mixed in a mass ratio of 29:0.5:71, melt-blended at 270°C for 25 minutes, and extruded and sheeted to obtain a highly elastic antibacterial PETG material.

[0073] Example 5

[0074] This embodiment discloses a method for preparing a highly elastic antibacterial PETG material, comprising the following steps:

[0075] (1) Graphene oxide, silver nitrate and water are mixed uniformly, ultrasonicated at a frequency of 40 kHz for 20 minutes, ascorbic acid is added, ultrasonicated at a frequency of 40 kHz for 50 minutes, the temperature is raised to 100° C., and the temperature is kept for reaction for 18 hours. After the reaction is completed, the mixture is filtered, washed with deionized water, and dried at 100° C. for 1 hour under a nitrogen atmosphere to obtain an antibacterial agent;

[0076] Among them, the mass ratio of graphene oxide, silver nitrate, water, and ascorbic acid is 7:2.6:750:40;

[0077] (2) The antibacterial agent, 3-aminopropyltriethoxysilane, and ethanol aqueous solution were mixed uniformly in a mass ratio of 3:1:100, ultrasonicated at a frequency of 40 kHz for 20 minutes, heated to 55°C for reaction for 75 minutes, and then heated to 75°C for reaction for 50 minutes. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with water, and dried at 100°C for 1 hour under a nitrogen atmosphere to obtain a modified antibacterial agent;

[0078] Wherein, the mass ratio of ethanol to water in the ethanol aqueous solution is 5:95;

[0079] (3) The modified antibacterial agent, amoxicillin, ethylenediamine, and acetone were uniformly mixed in a mass ratio of 7:6:0.6:40, and ultrasonicated at a frequency of 30 kHz for 30 min to obtain an antibacterial component dispersion;

[0080] (4) isophorone diisocyanate, polycaprolactone (relative molecular weight of 1000), and hydroxyalkyl silicone oil (relative molecular weight of 3000) are mixed evenly, stirred and heated to 90°C, reacted for 2.5 hours, cooled to 80°C after the reaction, added 2,2-dihydroxymethylbutyric acid and dibutyltin dilaurate, reacted for 2 hours, cooled to 50°C after the reaction, added antibacterial component dispersion, reacted for 0.5 hours, added deionized water until the solid precipitate no longer increased, filtered, and dried at 80°C for 5 hours to obtain a modified polyurethane-loaded antibacterial agent;

[0081] The mass ratio of the antibacterial component dispersion, isophorone diisocyanate, polycaprolactone, hydroxyalkyl silicone oil, 2,2-dihydroxymethylbutyric acid, and dibutyltin dilaurate is 65:250:400:600:65:11;

[0082] (5) The modified polyurethane loaded antibacterial agent, dibutyltin dilaurate, and PETG were uniformly mixed in a mass ratio of 30:0.5:70, melt-blended at 280°C for 20 min, and extruded and sheeted to obtain a highly elastic antibacterial PETG material.

[0083] Comparative Example 1

[0084] This comparative example discloses a method for preparing a highly elastic antibacterial PETG material, comprising the following steps:

[0085] (1) mixing amoxicillin, ethylenediamine, and acetone in a mass ratio of 5:0.6:44, and ultrasonicating at a frequency of 30 kHz for 30 min to obtain an antibacterial component dispersion;

[0086] (2) Diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone (relative molecular weight of 530), and hydroxyl silicone oil (relative molecular weight of 2000) were mixed evenly, stirred and heated to 90°C, reacted for 2.5 hours, cooled to 80°C after the reaction, added 1,4-butanediol and dibutyltin dilaurate, reacted for 2 hours, cooled to 50°C after the reaction, added antibacterial component dispersion, reacted for 0.5 hours, added deionized water until the solid precipitate no longer increased, filtered, and dried at 80°C for 5 hours to obtain a modified polyurethane antibacterial agent;

[0087] The mass ratio of the antibacterial component dispersion, diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone, hydroxyalkyl silicone oil, 1,4-butanediol, and dibutyltin dilaurate is 50:110:120:220:400:45:8;

[0088] (3) The modified polyurethane antibacterial agent, dibutyltin dilaurate, and PETG were uniformly mixed in a mass ratio of 26:0.5:74, melt-blended at 270°C for 25 minutes, and extruded and sheeted to obtain a highly elastic antibacterial PETG material.

[0089] Comparative Example 2

[0090] This comparative example discloses a method for preparing an antibacterial PETG material, comprising the following steps:

[0091] (1) Graphene oxide, silver nitrate and water are mixed uniformly, ultrasonicated at a frequency of 30 kHz for 30 minutes, ascorbic acid is added, ultrasonicated at a frequency of 30 kHz for 60 minutes, the temperature is raised to 95° C., and the temperature is kept for reaction for 19 hours. After the reaction is completed, the mixture is filtered, washed with deionized water, and dried at 90° C. for 1.5 hours under a nitrogen atmosphere to obtain an antibacterial agent;

[0092] Among them, the mass ratio of graphene oxide, silver nitrate, water, and ascorbic acid is 4:2.0:750:35;

[0093] (2) The antibacterial agent, n-butyltriethoxysilane, and ethanol aqueous solution were mixed uniformly in a mass ratio of 1.5:1:100, ultrasonicated at a frequency of 30 kHz for 30 minutes, heated to 50°C for reaction for 90 minutes, and then heated to 70°C for reaction for 60 minutes. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with water, and dried at 90°C for 1.5 hours under a nitrogen atmosphere to obtain a modified antibacterial agent;

[0094] Wherein, the mass ratio of ethanol to water in the ethanol aqueous solution is 5:95;

[0095] (3) The modified antibacterial agent and PETG were uniformly mixed in a mass ratio of 0.15:74, melt-blended at 270° C. for 25 min, and extruded and sheeted to obtain a highly elastic antibacterial PETG material.

[0096] Comparative Example 3

[0097] This comparative example discloses a method for preparing a highly elastic antibacterial PETG material, comprising the following steps:

[0098] (1) silver powder, 3-aminopropyltriethoxysilane, and ethanol aqueous solution were mixed uniformly in a mass ratio of 1.5:1:100, ultrasonicated at a frequency of 30 kHz for 30 min, heated to 50° C. for reaction for 90 min, and then heated to 70° C. for reaction for 60 min. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with water, and dried at 90° C. for 1.5 h under a nitrogen atmosphere to obtain a modified antibacterial agent;

[0099] Wherein, the mass ratio of ethanol to water in the ethanol aqueous solution is 5:95;

[0100] (3) The modified antibacterial agent, ethylenediamine, and acetone were uniformly mixed in a mass ratio of 4:0.6:44, and ultrasonicated at a frequency of 30 kHz for 30 min to obtain an antibacterial component dispersion;

[0101] (4) Diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone (relative molecular weight of 530), and hydroxyl silicone oil (relative molecular weight of 2000) were mixed evenly, stirred and heated to 90°C, reacted for 2.5 hours, cooled to 80°C after the reaction, added 1,4-butanediol and dibutyltin dilaurate, reacted for 2 hours, cooled to 50°C after the reaction, added antibacterial component dispersion, reacted for 0.5 hours, added deionized water until the solid precipitate no longer increased, filtered, and dried at 80°C for 5 hours to obtain a modified polyurethane-loaded antibacterial agent;

[0102] The mass ratio of the antibacterial component dispersion, diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone, hydroxyalkyl silicone oil, 1,4-butanediol, and dibutyltin dilaurate is 50:110:120:220:400:45:8;

[0103] (5) The modified polyurethane loaded antibacterial agent, dibutyltin dilaurate, and PETG were uniformly mixed in a mass ratio of 26:0.5:74, melt-blended at 270°C for 25 minutes, and extruded and sheeted to obtain a highly elastic antibacterial PETG material.

[0104] In all the above examples, graphene oxide comes from Jiangsu Xianfeng Nanotechnology Co., Ltd. with a product number of 103080; silver nitrate comes from Nanjing Chemical Reagent Service Co., Ltd. with a CAS number of 7761-88-8; ascorbic acid comes from Shanghai Yuanye Biotechnology Co., Ltd. with a CAS number of 50-81-7; 3-aminopropyltriethoxysilane comes from Shanghai Aladdin Biochemical Technology Co., Ltd. with a CAS number of 919-30-2; amoxicillin comes from Henan Kuanzhan Biotechnology Co., Ltd. with a CAS number of 26787-78-0; ethylenediamine comes from Shanghai Aladdin Biochemical Technology Co., Ltd. with a CAS number of 6780-13-8; acetone comes from Nanjing Chemical Reagent Co., Ltd. with a CAS number of 67-64-1; diphenylmethane diisocyanate comes from Shanghai McLean Biochemical Technology Co., Ltd. with a CAS number of 101-68-8; isophorone diisocyanate comes from Tesco Chemical The CAS number is 4098-71-9; polycaprolactone diol comes from Hunan Juren Chemical New Materials Co., Ltd., with the item numbers 2044 (molecular weight 400), 2053 (molecular weight 530), and 2102 (molecular weight 1000); hydroxyl silicone oil comes from Jiaxing United Chemical Co., Ltd., model UV-3667; 1.4-butanediol comes from Shanghai Jizhi Biochemical Technology Co., Ltd., with the CAS number 110-63-4; 2,2-dihydroxymethylbutyric acid comes from Shanghai MacLean Biochemical Technology Co., Ltd., with the CAS number 10097-02-6; PETG comes from Dongguan Hongchuang Plastic Co., Ltd., with the brand name JN200; silver powder comes from Ningbo Beigaer New Materials Co., Ltd., with the brand name beigaer and the particle size of 1-2μm; n-butyltriethoxysilane comes from Hebei Zhentian Food Additive Co., Ltd., with the CAS number 4781-99-1.

[0105] Test example

[0106] Test 1. Mechanical properties test: According to GB / T 1040-2018 "Determination of tensile properties of plastics", the tensile properties of the highly elastic antibacterial PETG materials prepared in Examples 1-5 and Comparative Examples 1-3 were measured to determine their tensile strength, elongation at break, and tensile elastic modulus. The test results are shown in Table 1, Table 2, and Table 3:

[0107] Table 1

[0108]

[0109] Table 2

[0110]

[0111] Table 3

[0112]

[0113] As shown in Table 1, Table 2 and Table 3, the PETG material prepared by the present invention has good mechanical properties and high elasticity. Antibacterial agent (graphene oxide loaded nano silver particles) as an inorganic filler can play a role of strengthening and toughening the matrix material and improve the mechanical properties of the material; polyurethane has excellent flexibility and elasticity, and can effectively increase the elasticity and elongation at break of PETG. Compared with Example 2, in Comparative Example 1, the antibacterial component dispersion only contains amoxicillin, does not contain antibacterial agent, lacks the role of strengthening and toughening of inorganic filler, and the tensile properties and elasticity of the matrix material are reduced; in Comparative Example 2, only modified antibacterial agent is added, and no polyurethane component is added, and the tensile properties and elasticity of the material are significantly reduced; in Comparative Example 3, only silver powder is modified as a modified antibacterial agent, and there is no obvious effect on the mechanical properties of the material, because silver powder, as an inorganic filler, can also play a role of strengthening and toughening the matrix material.

[0114] Test 2: Antibacterial performance test: According to QB / T 2591-2003 "Antibacterial Performance Test Method and Antibacterial Effect of Antibacterial Plastics", the high elastic antibacterial PETG materials prepared in Examples 1-5 and Comparative Examples 1-3 were tested for antibacterial performance, and their antibacterial performance and antibacterial performance after being placed for 50 days at a temperature of 50°C and a humidity of 80% were tested respectively. The test results are shown in Tables 4 and 5:

[0115] Table 4

[0116]

[0117] Table 5

[0118]

[0119] As shown in Table 4 and Table 5, the PETG material prepared by the present invention has good antibacterial properties. Graphene oxide has good antibacterial ability, and nanosilver particles can generate silver ions to play an antibacterial role. The two are used in combination to prepare an antibacterial agent (graphene oxide loaded with nanosilver particles), which effectively improves the antibacterial property; in addition, the introduction of amoxicillin with antibacterial properties forms a synergistic effect with the antibacterial agent, which can further improve the antibacterial property of the material. Compared with Example 2, in Comparative Example 1, the antibacterial component dispersion only contains amoxicillin and no antibacterial agent, and the antibacterial performance is reduced; in Comparative Example 2, only the modified antibacterial agent is added, and no amoxicillin is added, and the antibacterial performance is also reduced. After the material is placed at a temperature of 50°C and a humidity of 80% for 50 days, the antibacterial performance of the material is significantly reduced. This is because in an environment with high humidity, after the nanosilver is oxidized into silver ions, there is no amoxicillin in the matrix material to form a chelate, and it is easy to precipitate from the matrix material, resulting in silver ion loss, so the antibacterial performance of the material is significantly reduced; in Comparative Example 3, the antibacterial component only contains silver powder, and the antibacterial performance is significantly reduced; after the material is placed at a temperature of 50°C and a humidity of 80% for 50 days, since the silver powder is directly added to the matrix material and graphene oxide is not used to load the nanosilver, the nanosilver is easily oxidized into silver ions in an environment with high humidity and precipitates from the material, resulting in a significant reduction in antibacterial performance.

[0120] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a highly elastic antibacterial PETG material, characterized in that: The following steps are involved: Step (1), mixing graphene oxide, silver nitrate and water, ultrasonically dispersing, adding ascorbic acid, continuing ultrasonic dispersion, heating to react, filtering, washing and drying after the reaction to obtain an antibacterial agent; Wherein, the mass ratio of graphene oxide, silver nitrate, water and ascorbic acid is (3-7):(1.3-2.6):750:(32-40); Step (2), mixing the antibacterial agent, 3-aminopropyltriethoxysilane and ethanol aqueous solution, ultrasonically dispersing, heating to react, and after the reaction, continuing to heat to react, cooling to room temperature, filtering, washing and drying to obtain a modified antibacterial agent; Wherein, the mass ratio of the antibacterial agent, 3-aminopropyltriethoxysilane, and ethanol aqueous solution is (1-3):1:100; Step (3), uniformly mixing the modified antibacterial agent, amoxicillin, ethylenediamine and acetone, and ultrasonically dispersing the mixture to obtain an antibacterial component dispersion; Wherein, the mass ratio of the modified antimicrobial agent, amoxicillin, ethylenediamine and acetone is: (3-7): (4-6): 0.6: 40; The diisocyanate, polyester polyol and hydroxyl-terminated polysiloxane are mixed uniformly, stirred and heated to a first set temperature, reacted, cooled to a second reaction temperature, a chain extender and a catalyst are added, reacted, cooled to a third reaction temperature, an antibacterial component dispersion is added, reacted, and after the reaction is completed, precipitated, filtered, and dried to obtain a modified polyurethane-loaded antibacterial agent; The mass ratio of the antibacterial component dispersion, diisocyanate, polyester polyol, hydroxyl-terminated polysiloxane, chain extender and catalyst is: (50-65): (220-250): (160-400): (300-600): (35-65): (7-11); Step (4), melt-blending the modified polyurethane loaded antibacterial agent, dibutyltin dilaurate, and PETG, and extruding and tableting to obtain a high-elasticity antibacterial PETG material; The mass ratio of the modified polyurethane loaded antibacterial agent, dibutyltin dilaurate and PETG is: (25-30):0.5:(70-75).

2. The method for preparing a highly elastic antibacterial PETG material according to claim 1, characterized in that: In the step (1), the temperature reaction condition is: reacting at a temperature of 90-100° C. for 18-20 hours; the ultrasonic dispersion condition is: ultrasonicating at a frequency of 20-40 kHz for 20-40 minutes, the ultrasonic dispersion condition is: ultrasonicating at a frequency of 20-40 kHz for 50-70 minutes, and the drying condition is: drying at 80-100° C. for 1-2 hours under a nitrogen atmosphere.

3. The method for preparing a highly elastic antibacterial PETG material according to claim 1, characterized in that: In the step (2), the mass ratio of ethanol to water in the ethanol aqueous solution is 5:

95.

4. The method for preparing a highly elastic antibacterial PETG material according to claim 1, characterized in that: In the step (2), the conditions for ultrasonic dispersion are: ultrasonication at a frequency of 20-40 kHz for 20-40 minutes, the conditions for temperature increase reaction are: reaction at a temperature of 45-55°C for 75-105 minutes, the conditions for continued temperature increase reaction are: reaction at a temperature of 65-75°C for 50-70 minutes, and the conditions for drying are: drying at 80-100°C for 1-2 hours under a nitrogen atmosphere.

5. The method for preparing a highly elastic antibacterial PETG material according to claim 1, characterized in that: In the step (3), the diisocyanate is at least one of diphenylmethane diisocyanate and isophorone diisocyanate, the polyester polyol is polycaprolactone diol with a relative molecular weight of 400-1000, the hydroxyl-terminated polysiloxane is hydroxyalkyl silicone oil with a relative molecular weight of 2000-3000, the chain extender is at least one of 1,4-butanediol and 2,2-dihydroxymethylbutyric acid, and the catalyst is dibutyltin dilaurate.

6. The method for preparing a highly elastic antibacterial PETG material according to claim 1, characterized in that: In the step (3), the conditions for ultrasonic dispersion are: ultrasound at a frequency of 20-40 kHz for 20-40 minutes, the first set temperature is 85-95°C, the reaction time is 2-3 hours, the second reaction temperature is 75-85°C, the reaction time is 1.5-2.5 hours, the third reaction temperature is 50°C, the reaction time is 0.5 hours, the precipitation agent is deionized water, and the drying conditions are: drying at 70-90°C for 4-6 hours.

7. The method for preparing a highly elastic antibacterial PETG material according to claim 1, characterized in that: In the step (4), the temperature of melt blending is 260-280°C, and the blending time is 20-30 minutes.

8. A high elasticity antibacterial PETG material prepared by the method for preparing a high elasticity antibacterial PETG material as claimed in any one of claims 1 to 7.

9. An application of the highly elastic antibacterial PETG material as claimed in claim 8 in medical packaging, characterized in that: Medical packaging material prepared based on the high-elasticity antibacterial PETG material.

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