A FDM type 3D printing antibacterial material and its preparation process

Abstract

The present invention relates to the technical field of 3D printing materials, specifically to a FDM type 3D printing antibacterial material and a preparation process thereof. The antibacterial material comprises the following weight components: 100-110 parts of multi-arm polylactic acid, 5-15 parts of modified ricinoleic acid, 1-5 parts of maleic anhydride, 0.5-1.0 parts of benzoyl peroxide, 2-8 parts of antibacterial agent, and 1-4 parts of modified zinc oxide. The present invention obtains modified polylactic acid by reacting multi-arm polylactic acid, modified ricinoleic acid, maleic anhydride and benzoyl peroxide; the modified polylactic acid, antibacterial agent and modified zinc oxide are uniformly mixed, and a 3D printing antibacterial material is obtained by melting, extruding and drawing. The 3D printing antibacterial material prepared by the present invention has excellent mechanical properties and antibacterial properties, and is flame retardant.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing materials, and in particular to an FDM type 3D printing antibacterial material and a preparation process thereof. Background Art

[0002] In recent years, the use of disposable plastic products has been restricted, and green and environmentally friendly biodegradable materials and their composite materials have ushered in new development opportunities and challenges. Fused deposition modeling (FDM) 3D printing is a rapid additive manufacturing technology based on the layer-by-layer accumulation of molten thermoplastic polymers, which can form products of complex shapes without the need for molds.

[0003] As one of the representatives of biodegradable polymers with excellent properties such as high strength, high modulus, and biocompatibility, polylactic acid also has good shape memory properties. However, the disadvantages of polylactic acid, such as high brittleness, poor toughness, and low melt strength, also limit its application. In the application of biodegradable materials, they are susceptible to erosion and contamination by bacteria and fungi, and antibacterial properties have become an important consideration. At present, the enhancement of antibacterial properties still faces challenges in the field of biodegradable materials, including the durability of the antibacterial effect, the wide range of antibacterial effects, and the stability of antibacterial materials. Issues need to be solved urgently.

[0004] Therefore, we propose an FDM-type 3D printing antibacterial material and its preparation process. Summary of the invention

[0005] The purpose of the present invention is to provide an FDM type 3D printing antibacterial material and a preparation process thereof to solve the problems raised in the above background technology.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] A preparation process of an FDM type 3D printing antibacterial material comprises the following steps:

[0008] Step S1: evenly mixing multi-arm polylactic acid, modified ricinoleic acid, maleic anhydride and benzoyl peroxide, reacting at 100-110° C. for 4-6 hours, filtering, washing and drying to obtain modified polylactic acid;

[0009] Step S2: uniformly mix the modified polylactic acid, the antibacterial agent, and the modified zinc oxide, and obtain a 3D printing antibacterial material by melting, extruding, and drawing.

[0010] Furthermore, the antibacterial material comprises the following components by weight: 100-110 parts of multi-arm polylactic acid, 5-15 parts of modified ricinoleic acid, 1-5 parts of maleic anhydride, 0.5-1.0 parts of benzoyl peroxide, 2-8 parts of antibacterial agent, and 1-4 parts of modified zinc oxide.

[0011] Furthermore, the preparation method of the multi-arm polylactic acid is as follows:

[0012] The lactic acid is heated to 110-120° C. and reacted under vacuum for 3-5 hours to obtain lactic acid oligomers; the lactic acid oligomers, stannous octoate and pentaerythritol are evenly mixed, vacuumed and filled with nitrogen, reacted at 160-180° C. for 8-10 hours, and after filtering, washing and drying, multi-arm polylactic acid is obtained.

[0013] Furthermore, the multi-arm polylactic acid comprises the following components by weight: 100-110 parts of lactic acid, 5-15 parts of pentaerythritol, and 0.5-1.0 parts of stannous octoate.

[0014] Furthermore, the preparation method of the modified ricinoleic acid is as follows:

[0015] Under nitrogen protection, ricinoleic acid, epichlorohydrin and triethylamine are mixed evenly, reacted at 100-110°C for 3-5h, cooled to 60-65°C, potassium hydroxide is added, and the reaction is continued for 2-4h. After filtering, washing and drying, modified ricinoleic acid is obtained.

[0016] Furthermore, the modified ricinoleic acid comprises the following components by weight: 5-15 parts of ricinoleic acid, 25-60 parts of epichlorohydrin, 0.03-0.08 parts of triethylamine, and 2-8 parts of potassium hydroxide.

[0017] Furthermore, the preparation method of the antibacterial agent is as follows:

[0018] Step (1): mix eugenol and ethyl acetate evenly, add triethylamine and mix evenly, cool in an ice bath for 10-20 minutes, add a mixed solution of phenyl dichlorophosphate and ethyl acetate, stir at room temperature for 22-24 hours, filter, wash and dry to obtain a flame retardant;

[0019] Step (2): evenly mix carboxymethyl chitosan and deionized water to obtain a carboxymethyl chitosan solution; evenly mix silver nitrate and deionized water to obtain a silver nitrate solution; evenly mix the carboxymethyl chitosan solution and the nitrate solution, add sodium hydroxide solution to adjust the system pH to 10-11, and react at 70-80°C for 4-6 hours to obtain a complex;

[0020] The complex is added to a mixed solution of acetonitrile and deionized water, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and mercaptopropionic acid are added and mixed evenly, reacted for 10-12 hours in the dark, filtered, washed, and dried to obtain a thiolated complex;

[0021] Step (3): uniformly mix the flame retardant, the thiol compound and the photoinitiator, and obtain the antibacterial agent after ultraviolet irradiation.

[0022] In the above technical scheme, eugenol and dichlorophenyl phosphate react to obtain a bio-based flame retardant containing two carbon-carbon double bonds; then, carboxymethyl chitosan is used to reduce silver nitrate, and the carboxyl and hydroxyl groups of the carboxymethyl chitosan chelate the silver ions and reduce them to silver nanoparticles. At the same time, the carboxymethyl chitosan wraps the formed silver nanoparticles in a network, controls their nucleation and growth, forms an insoluble complex, and plays a role as a stabilizer, thereby obtaining carboxymethyl chitosan / silver nanoparticles, i.e., a composite; then, the remaining amino groups in the carboxymethyl chitosan are used to undergo an amidation reaction with the carboxyl groups of mercaptopropionic acid, and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide is used for cross-linking, so that a large number of thiols can be grafted onto the composite, which can provide abundant active sites; finally, the double bonds in the flame retardant and the thiol-containing composite undergo a thiol-ene click reaction to obtain an antibacterial agent with a flame retardant effect.

[0023] Furthermore, in step (1), the mass ratio of eugenol, ethyl acetate and triethylamine is 1:(4-5):(0.6-0.8).

[0024] Furthermore, in step (1), the mass of phenyl dichloride phosphate is 0.6-0.8 times the mass of eugenol, and the mass ratio of phenyl dichloride phosphate to ethyl acetate is 1:(1.4-1.6).

[0025] Furthermore, in step (2), the concentration of the carboxymethyl chitosan solution is 0.5 wt %, the concentration of the silver nitrate solution is 5 mg / mL, and the volume ratio of the carboxymethyl chitosan solution to the nitrate solution is 10:1.

[0026] Furthermore, in step (2), the mass ratio of the complex, acetonitrile, deionized water, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and mercaptopropionic acid is 1:(2-3):(15-30):(1.0-1.2):(0.7-1.2).

[0027] Furthermore, in the step (3), the mass ratio of the flame retardant, the thiol compound and the photoinitiator is 1:(2-4):(0.3-0.5).

[0028] Furthermore, the photoinitiator is 2-hydroxy-2-methylpropiophenone.

[0029] Furthermore, the process conditions of the ultraviolet irradiation are: irradiation wavelength 360-400nm, irradiation time 0.5-2h, irradiation intensity 20-35mW / cm 2 .

[0030] Furthermore, the modified zinc oxide is amino-modified nano zinc oxide.

[0031] Furthermore, in step S2, the melting temperature is 170-190°C.

[0032] Furthermore, in step S2, the extrusion temperature is 190-200°C.

[0033] Furthermore, in step S2, the average diameter of the 3D printed antibacterial material is 1.7-3.5 mm.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] 1. A FDM type 3D printing antibacterial material and its preparation process of the present invention, with pentaerythritol as the core molecule, polymerized with lactic acid to form multi-arm polylactic acid, introducing hydroxyl groups, effectively improving the hydrophilicity of polylactic acid; compared with linear polylactic acid, the multi-arm polylactic acid prepared by the present invention has a branched structure, which can improve the melt strength and crystallinity of polylactic acid; by epoxidation modification of ricinoleic acid, a modified ricinoleic acid with double bonds and epoxy groups is obtained, and modified ricinoleic acid and maleic anhydride are used as co-grafting monomers, and benzoyl peroxide is used as an initiator to react with hydrogen atoms on the tertiary carbon of polylactic acid chain to form a multi-arm polylactic acid with epoxy groups, i.e., modified polylactic acid, which effectively improves brittleness and further improves the mechanical strength and flow properties of the material. At the same time, the epoxy group in the modified polylactic acid can react with the amino group in the modified zinc oxide, which enhances the compatibility between the two, helps to improve the antibacterial effect and stability, and makes the antibacterial material more reliable.

[0036] 2. An FDM type 3D printing antibacterial material and a preparation process thereof of the present invention, wherein eugenol and phenyl dichloride phosphate react to introduce double bonds to obtain a phosphorus-containing bio-based flame retardant, wherein eugenol is a natural organic compound with the efficacy of inhibiting bacteria and antioxidant effects, and can improve the antibacterial and antioxidant properties of the material; carboxymethyl chitosan is used to reduce silver nitrate to obtain carboxymethyl chitosan / silver nanoparticles, i.e., a composite, which has a strong antibacterial effect and can kill bacteria and other microorganisms. Carboxymethyl chitosan as a carrier helps to stabilize the silver nanoparticles and improve their antibacterial effect, and then mercaptopropionic acid is used as a modifier and 1-ethyl-(3-dimethylaminopropyl) carbodiimide is used as an activator to graft thiol groups onto the composite to obtain a thiol-containing composite; the double bonds in the flame retardant and the thiol-containing composite undergo a thiol-ene click reaction to obtain an antibacterial agent with both flame retardant and antibacterial effects, which can effectively inhibit bacterial growth while improving the flame retardant properties of the material. The present invention adopts a combination of an antibacterial agent and modified zinc oxide to significantly improve the antibacterial properties of the material through a synergistic effect. At the same time, this combination also shows good compatibility with modified polylactic acid, further enhancing the functionality and stability of the material. The addition of an antibacterial agent can effectively inhibit the growth of microorganisms, while modified zinc oxide provides excellent antibacterial properties. The combined effect of the two makes the material outstanding in terms of antibacterial performance. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] The modified zinc oxide in this embodiment is amino-modified nano zinc oxide, model MYH-GZY50, which comes from Xuzhou Mingyanhai New Materials Technology Co., Ltd.

[0039] In the following examples and comparative examples, 1 part is equal to 10 g.

[0040] Embodiment 1: A preparation process of an FDM type 3D printing antibacterial material, comprising the following processes:

[0041] Step S1: 100 parts of multi-arm polylactic acid, 5 parts of modified ricinoleic acid, 1 part of maleic anhydride and 0.5 parts of benzoyl peroxide are mixed evenly, reacted at 100° C. for 4 hours, filtered, washed and dried to obtain modified polylactic acid;

[0042] Step S2: uniformly mix the modified polylactic acid, 2 parts of the antibacterial agent, and 1 part of the modified zinc oxide, add the mixture into a twin-screw extruder, and obtain a 3D printing antibacterial material by melting (temperature of 170° C.), extruding (temperature of 190° C.), and drawing.

[0043] The preparation method of modified ricinoleic acid is as follows:

[0044] Under nitrogen protection, 5 parts of ricinoleic acid, 25 parts of epichlorohydrin and 0.03 parts of triethylamine were mixed evenly, reacted at 100°C for 3 hours, cooled to 60°C, 2 parts of potassium hydroxide were added, and the reaction was continued for 2 hours. After filtering, washing and drying, modified ricinoleic acid was obtained;

[0045] The preparation method of the antibacterial agent is as follows:

[0046] Step (1): 2 parts of eugenol and 8 parts of ethyl acetate are mixed evenly, 1.2 parts of triethylamine are added and mixed evenly, the mixture is cooled in an ice bath for 10 minutes, 1.2 parts of a mixed solution of phenyl dichlorophosphate and 1.68 parts of ethyl acetate are added, the mixture is stirred at room temperature for 22 hours, and a flame retardant is obtained after filtering, washing and drying;

[0047] Step (2): mix carboxymethyl chitosan and deionized water to obtain a 0.5 wt% carboxymethyl chitosan solution; mix silver nitrate and deionized water to obtain a 5 mg / mL silver nitrate solution; mix the carboxymethyl chitosan solution and the nitrate solution in a volume ratio of 10:1, add sodium hydroxide solution to adjust the system pH to 10, and react at 70°C for 4 hours to obtain a composite;

[0048] 4 parts of the complex were added to a mixed solution of 8 parts of acetonitrile and 60 parts of deionized water, 4 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and 2.8 parts of mercaptopropionic acid were added and mixed evenly, reacted for 10 hours in the dark, and filtered, washed and dried to obtain a thiolated complex;

[0049] Step (3): 2 parts of flame retardant, 4 parts of thiol compound and 0.6 parts of photoinitiator were mixed evenly and irradiated with ultraviolet light (irradiation wavelength 360nm, irradiation time 0.5h, irradiation intensity 20mW / cm 2 ), to obtain an antibacterial agent.

[0050] Embodiment 2: A preparation process of an FDM type 3D printing antibacterial material, comprising the following processes:

[0051] Step S1: 105 parts of multi-arm polylactic acid, 10 parts of modified ricinoleic acid, 3 parts of maleic anhydride and 0.8 parts of benzoyl peroxide are mixed evenly, reacted at 105° C. for 5 hours, filtered, washed and dried to obtain modified polylactic acid;

[0052] Step S2: uniformly mix the modified polylactic acid, 6 parts of the antibacterial agent, and 3 parts of the modified zinc oxide, add the mixture into a twin-screw extruder, and obtain a 3D printing antibacterial material by melting (temperature of 180° C.), extruding (temperature of 195° C.), and drawing.

[0053] The preparation method of modified ricinoleic acid is as follows:

[0054] Under nitrogen protection, 10 parts of ricinoleic acid, 50 parts of epichlorohydrin and 0.05 parts of triethylamine were mixed evenly, reacted at 105°C for 4 hours, cooled to 63°C, 6 parts of potassium hydroxide were added, and the reaction was continued for 3 hours. After filtering, washing and drying, modified ricinoleic acid was obtained;

[0055] The preparation method of the antibacterial agent is as follows:

[0056] Step (1): 2 parts of eugenol and 9 parts of ethyl acetate are mixed evenly, 1.4 parts of triethylamine are added and mixed evenly, the mixture is cooled in an ice bath for 15 minutes, 1.4 parts of a mixed solution of phenyl dichlorophosphate and 2.1 parts of ethyl acetate are added, the mixture is stirred at room temperature for 23 hours, and a flame retardant is obtained after filtering, washing and drying;

[0057] Step (2): mix carboxymethyl chitosan and deionized water to obtain a 0.5 wt% carboxymethyl chitosan solution; mix silver nitrate and deionized water to obtain a 5 mg / mL silver nitrate solution; mix the carboxymethyl chitosan solution and the nitrate solution in a volume ratio of 10:1, add sodium hydroxide solution to adjust the system pH to 10.5, and react at 75°C for 5 hours to obtain a composite;

[0058] 6 parts of the complex were added to a mixed solution of 15 parts of acetonitrile and 120 parts of deionized water, 6.6 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and 6 parts of mercaptopropionic acid were added and mixed evenly, reacted for 11 hours in the dark, and filtered, washed and dried to obtain a thiolated complex;

[0059] Step (3): 2 parts of flame retardant, 6 parts of thiol compound and 0.8 parts of photoinitiator were mixed evenly and irradiated with ultraviolet light (irradiation wavelength 380nm, irradiation time 1h, irradiation intensity 30mW / cm 2 ), to obtain an antibacterial agent.

[0060] Embodiment 3: A preparation process of an FDM type 3D printing antibacterial material, comprising the following processes:

[0061] Step S1: 110 parts of multi-arm polylactic acid, 15 parts of modified ricinoleic acid, 5 parts of maleic anhydride and 1.0 part of benzoyl peroxide are mixed evenly, reacted at 110° C. for 6 hours, filtered, washed and dried to obtain modified polylactic acid;

[0062] Step S2: uniformly mix the modified polylactic acid, 8 parts of the antibacterial agent, and 4 parts of the modified zinc oxide, add the mixture into a twin-screw extruder, and perform melting (temperature of 190° C.), extrusion (temperature of 200° C.), and wire drawing to obtain a 3D printing antibacterial material;

[0063] The preparation method of modified ricinoleic acid is as follows:

[0064] Under nitrogen protection, 15 parts of ricinoleic acid, 60 parts of epichlorohydrin and 0.08 parts of triethylamine were mixed evenly, reacted at 110°C for 5 hours, cooled to 65°C, 8 parts of potassium hydroxide were added, and the reaction was continued for 4 hours. After filtering, washing and drying, modified ricinoleic acid was obtained;

[0065] The preparation method of the antibacterial agent is as follows:

[0066] Step (1): 2 parts of eugenol and 10 parts of ethyl acetate are mixed evenly, 1.6 parts of triethylamine are added and mixed evenly, the mixture is cooled in an ice bath for 20 minutes, 1.6 parts of a mixed solution of phenyl dichlorophosphate and 2.56 parts of ethyl acetate are added, the mixture is stirred at room temperature for 24 hours, and a flame retardant is obtained after filtering, washing and drying;

[0067] Step (2): mix carboxymethyl chitosan and deionized water to obtain a 0.5 wt% carboxymethyl chitosan solution; mix silver nitrate and deionized water to obtain a 5 mg / mL silver nitrate solution; mix the carboxymethyl chitosan solution and the nitrate solution in a volume ratio of 10:1, add sodium hydroxide solution to adjust the system pH to 11, and react at 80°C for 6 hours to obtain a composite;

[0068] 8 parts of the complex were added to a mixed solution of 24 parts of acetonitrile and 240 parts of deionized water, and 9.6 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and 9.6 parts of mercaptopropionic acid were added and mixed evenly, and reacted for 12 hours in the dark, and filtered, washed, and dried to obtain a thiolated complex;

[0069] Step (3): 2 parts of flame retardant, 8 parts of thiol compound and 1 part of photoinitiator were mixed evenly and irradiated with ultraviolet light (irradiation wavelength 400nm, irradiation time 2h, irradiation intensity 35mW / cm 2 ), to obtain an antibacterial agent.

[0070] Comparative Example 1: The antibacterial material includes the following components by weight: 105 parts of multi-arm polylactic acid, 10 parts of modified ricinoleic acid, 3 parts of maleic anhydride, 0.8 parts of benzoyl peroxide, 6 parts of the composite, and 3 parts of modified zinc oxide. In Comparative Example 1, the antibacterial agent is replaced with the composite of the same mass, and the other steps and processes are the same as those in Example 2.

[0071] Comparative Example 2: The antibacterial material includes the following components by weight: 105 parts of multi-arm polylactic acid, 10 parts of ricinoleic acid, 3 parts of maleic anhydride, 0.8 parts of benzoyl peroxide, 6 parts of antibacterial agent, and 3 parts of modified zinc oxide. In Comparative Example 2, the modified ricinoleic acid is replaced with ricinoleic acid of the same mass, and the other steps and processes are the same as those in Example 2.

[0072] Comparative Example 3: The antibacterial material includes the following components by weight: 105 parts of multi-arm polylactic acid, 10 parts of modified ricinoleic acid, 3 parts of maleic anhydride, 0.8 parts of benzoyl peroxide, and 3 parts of modified zinc oxide. No antibacterial agent is added in Comparative Example 3, and other steps and processes are the same as Example 2.

[0073] Comparative Example 4: A preparation process of an FDM type 3D printing antibacterial material, comprising the following processes:

[0074] The preparation method of the antibacterial agent is as follows:

[0075] Step (1): 2 parts of eugenol and 9 parts of ethyl acetate are mixed evenly, 1.4 parts of triethylamine are added and mixed evenly, the mixture is cooled in an ice bath for 15 minutes, 1.4 parts of a mixed solution of phenyl dichlorophosphate and 2.1 parts of ethyl acetate are added, the mixture is stirred at room temperature for 23 hours, and a flame retardant is obtained after filtering, washing and drying;

[0076] Step (2): mix carboxymethyl chitosan and deionized water to obtain a 0.5 wt% carboxymethyl chitosan solution; mix silver nitrate and deionized water to obtain a 5 mg / mL silver nitrate solution; mix the carboxymethyl chitosan solution and the nitrate solution in a volume ratio of 10:1, add sodium hydroxide solution to adjust the system pH to 10.5, and react at 75°C for 5 hours to obtain a composite;

[0077] 6 parts of the complex were added to a mixed solution of 15 parts of acetonitrile and 120 parts of deionized water, 6.6 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and 6 parts of mercaptopropionic acid were added and mixed evenly, reacted for 11 hours in the dark, and filtered, washed and dried to obtain a thiolated complex;

[0078] Step (3): 2 parts of flame retardant, 10 parts of thiol compound and 0.8 parts of photoinitiator were mixed evenly and irradiated with ultraviolet light (irradiation wavelength 380nm, irradiation time 1h, irradiation intensity 30mW / cm 2 ), to obtain an antibacterial agent;

[0079] Compared with Example 2, the mass ratio of the flame retardant to the thiol compound in Comparative Example 4 is 1:5; the other steps are the same as those in Example 2.

[0080] Experiment: Take the 3D printed antibacterial materials obtained in Examples 1-3 and Comparative Examples 1-4, use an FDM 3D printer to print samples, test their properties and record the test results:

[0081] The tensile properties were tested according to ISO 527-2-2012 1BA standard, the sample size was 75mm×10mm×2mm, and the test speed was 5mm / min. The flame retardancy was tested according to the vertical combustion method of UL94 standard, and the sample size was 125mm×13mm×1mm. Antibacterial rate test: the antibacterial performance was tested according to GB / T 31402-2015 standard, the sample size was 50mm×50mm×5mm, and the bacteria used were Escherichia coli ATCC 8739.

[0082] Test Results

[0083]

[0084] According to the data in the above table, we can clearly draw the following conclusions:

[0085] 1. Compared with Examples 1-3, the flame retardant properties of the product obtained in Comparative Example 1 are reduced, and it can be seen that the antibacterial agent prepared by the present invention has better flame retardant effect than the composite; the tensile properties and antibacterial properties of the product obtained in Comparative Example 2 are reduced, indicating that the present invention helps to improve the compatibility of polylactic acid with other components by adding modified ricinoleic acid and grafting epoxy groups onto multi-arm polylactic acid, thereby improving the mechanical properties and antibacterial properties of the material.

[0086] 2. Compared with Examples 1-3, the product obtained in Comparative Example 3 showed a decrease in both flame retardancy and antibacterial properties, which indicates that the antibacterial agent prepared by the present invention has dual flame retardancy and antibacterial effects, can effectively inhibit bacterial growth and improve the flame retardancy of the material.

[0087] 3. Compared with Examples 1-3, the flame retardancy and antibacterial rate of the product obtained in Comparative Example 4 are both reduced. It can be seen that the performance of the antibacterial agent prepared by the present invention is affected by the ratio of each reagent in its preparation process. By selecting the mass ratio within the said range, the prepared antibacterial agent has a more excellent effect.

[0088] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process method article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process method article or device.

[0089] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is 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 can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A preparation process of FDM type 3D printing antibacterial material, characterized by: The steps include: Step S1: evenly mixing multi-arm polylactic acid, modified ricinoleic acid, maleic anhydride and benzoyl peroxide, reacting at 100-110° C. for 4-6 hours, filtering, washing and drying to obtain modified polylactic acid; Step S2: uniformly mixing the modified polylactic acid, the antibacterial agent, and the modified zinc oxide, and performing melting, extrusion, and drawing to obtain a 3D printing antibacterial material; The preparation method of the modified ricinoleic acid is as follows: Under nitrogen protection, ricinoleic acid, epichlorohydrin and triethylamine are mixed evenly, reacted at 100-110°C for 3-5h, cooled to 60-65°C, potassium hydroxide is added, and the reaction is continued for 2-4h. After filtering, washing and drying, modified ricinoleic acid is obtained; The preparation method of the antibacterial agent is as follows: Step (1): mix eugenol and ethyl acetate evenly, add triethylamine and mix evenly, cool in an ice bath for 10-20 minutes, add a mixed solution of phenyl dichlorophosphate and ethyl acetate, stir at room temperature for 22-24 hours, filter, wash and dry to obtain a flame retardant; Step (2): evenly mix carboxymethyl chitosan and deionized water to obtain a carboxymethyl chitosan solution; evenly mix silver nitrate and deionized water to obtain a silver nitrate solution; evenly mix the carboxymethyl chitosan solution and the nitrate solution, add sodium hydroxide solution to adjust the system pH to 10-11, and react at 70-80°C for 4-6 hours to obtain a complex; The complex is added to a mixed solution of acetonitrile and deionized water, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and mercaptopropionic acid are added and mixed evenly, reacted for 10-12 hours in the dark, filtered, washed, and dried to obtain a thiolated complex; Step (3): uniformly mixing the flame retardant, the thiol compound and the photoinitiator, and irradiating the mixture with ultraviolet light to obtain an antibacterial agent; The modified zinc oxide is amino-modified nano zinc oxide.

2. The preparation process of a FDM type 3D printing antibacterial material according to claim 1, characterized in that: The antibacterial material comprises the following components by weight: 100-110 parts of multi-arm polylactic acid, 5-15 parts of modified ricinoleic acid, 1-5 parts of maleic anhydride, 0.5-1.0 parts of benzoyl peroxide, 2-8 parts of antibacterial agent and 1-4 parts of modified zinc oxide.

3. The preparation process of a FDM type 3D printing antibacterial material according to claim 2, characterized in that: The preparation method of the multi-arm polylactic acid is as follows: The lactic acid is heated to 110-120° C. and reacted under vacuum for 3-5 hours to obtain lactic acid oligomers; the lactic acid oligomers, stannous octoate and pentaerythritol are evenly mixed, vacuumed and filled with nitrogen, reacted at 160-180° C. for 8-10 hours, and after filtering, washing and drying, multi-arm polylactic acid is obtained.

4. The preparation process of a FDM type 3D printing antibacterial material according to claim 3, characterized in that: The multi-arm polylactic acid comprises the following components by weight: 100-110 parts of lactic acid, 5-15 parts of pentaerythritol, and 0.5-1.0 parts of stannous octoate.

5. The preparation process of a FDM type 3D printing antibacterial material according to claim 1, characterized in that: The modified ricinoleic acid comprises the following components by weight: 5-15 parts of ricinoleic acid, 25-60 parts of epichlorohydrin, 0.03-0.08 parts of triethylamine, and 2-8 parts of potassium hydroxide.

6. The preparation process of a FDM type 3D printing antibacterial material according to claim 1, characterized in that: In the step (1), the mass of phenyl dichloride phosphate is 0.6-0.8 times the mass of eugenol, and the mass ratio of phenyl dichloride phosphate to ethyl acetate is 1:(1.4-1.6).

7. The preparation process of a FDM type 3D printing antibacterial material according to claim 1, characterized in that: In the step S2, the extrusion temperature is 190-200°C.

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