CN109504048B - Thermotropic reversible crosslinking composition modified polylactic acid 3D printing wire and preparation method thereof - Google Patents
Thermotropic reversible crosslinking composition modified polylactic acid 3D printing wire and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of polylactic acid high-molecular 3D printing wire preparation, and particularly relates to a thermotropic reversible crosslinking composition modified polylactic acid 3D printing wire and a preparation method thereof. The 3D printing material prepared from polylactic acid has poor heat resistance, is easy to deform in the application field with slightly high temperature and is difficult to apply, and the invention adopts the thermoreversible crosslinking composition to modify the polylactic acid in combination with the requirement of FDM printing on the rheological property of the material, and adds functional additives such as a flowing agent, a toughening agent, a pigment and the like into a modified system to prepare the FDM printing wire with stable wire diameter, smooth surface and excellent heat resistance. When the FDM method is adopted for printing, the material is extruded stably, the surface of the prepared 3D printing device is smooth and flat, deformation is avoided, and the heat resistance and the mechanical property of the material are obviously improved after the printed device is placed in a dry and room-temperature environment for 7 days.
Description
Technical Field
The invention belongs to the field of polylactic acid high-molecular 3D printing wire preparation, and particularly relates to a thermotropic reversible crosslinking composition modified polylactic acid 3D printing wire and a preparation method thereof.
Background
Polylactic acid PLA is a degradable polymer material, and is the most popular 3D printing material at present because of the advantages of low printing temperature, no toxic gas generated during printing, difficult warping and deformation of devices after printing and the like. However, the heat resistance of the existing PLA printing wire is poor, and the thermal deformation temperature and the glass transition temperature are lower than 60 ℃, so that the PLA printing wire is difficult to be applied to personalized customized products with high requirements on the heat resistance of the material, and the application of the polylactic acid 3D printing material and the popularization of the 3D printing technology are greatly limited.
Nanofillers, carbon nanotubes, glass fibers, materials with higher heat resistance and chemical crosslinking methods are commonly used to improve the heat resistance of PLA, but unlike traditional molding methods such as injection molding, blow molding and calendering, the printing performance of 3D printed materials has higher requirements on the materials, especially on the rheological properties of the materials, and the improvement of the heat resistance of PLA materials must not be at the expense of reducing the rheological properties of the materials.
Patent CN103665802A discloses a method for modifying PLA by grinding polylactic acid and inorganic nanopowder, but because of the problem of the volume of the grinding machine, the amount of each grinding is very small, and the processing efficiency of this method is extremely low, and it is not applicable to industrial production. In the patent CN106700457A, a 3D printing material with good heat resistance is obtained by adding 2-10 parts of filler, 1-5 parts of cross-linking agent and stabilizer in a polylactic acid/Polycaprolactone (PCL) composite system and adopting double-screw extrusion and wire drawing. Patent CN104987680B discloses a method for preparing a high-strength and high-heat-resistance polylactic acid material for 3D printing by using an inorganic filler, a metal salt of a polycarboxylic acid and an amide compound to modify polylactic acid. Patent CN104031304B discloses a method for modifying polymer resin by using ultraviolet cross-linking agent and powder, wherein the cross-linking agent absorbs ultraviolet initiator with specific wavelength to generate high molecular chain free radical, so that the polymer is cross-linked in the 3D printing process to form a three-dimensional network structure, thereby improving the heat resistance of thermoplastic 3D printing materials such as PLA. However, the relatively strong hydrogen bonding between the inorganic filler, the crosslinking compound, especially the metal salt of polycarboxylic acid and the amide compound, is very easy to increase the viscosity of the polylactic acid material in a molten state, and is not favorable for FDM printing.
Patent CN108472889A discloses a method and system for improving the heat resistance of 3D printed objects by modifying the crystalline properties of 3D printed materials, wherein at least one reversible gelation medium is added into the system, which can promote the 3D printed objects to increase the crystallinity of the material of the objects during annealing process, so as to achieve the purpose of improving the heat resistance, but the annealing process easily causes the 3D printed objects to deform, and at the same time, the process of manufacturing personalized devices by 3D printing is added, which is not beneficial to industrial production.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention provides a 3D printing wire modified by a thermoreversible crosslinking composition.
The invention also aims to provide a preparation method of the polylactic acid 3D printing material modified by the thermoreversible crosslinking composition.
The purpose of the invention is realized by the following scheme:
A3D printing wire rod of polylactic acid modified by a thermoreversible crosslinking composition comprises the following components in parts by mass:
preferably, the fluidity modifier is one or more of a fluidity modifier YP-803, a fluidity modifier FA-700, a silicone powder 501 (Chinakawa Chinakai chemical engineering Co., Ltd., Guangzhou), a fluidity modifier FJ-100, a fluidity modifier FJ-200, a fluidity modifier FJ-300 and a fluidity modifier FJ-400;
preferably, the pigment is one or more than two of 100-400-mesh glitter powder, pearl powder, copper gold powder, iron oxide red, iron oxide yellow, phthalocyanine green, cobalt blue, iron chromium black and aluminum silver powder.
Preferably, the toughening agent is one or two of a toughening agent YF6030, a toughening agent YP-501, a toughening agent B308T, a toughening agent A-869 and a toughening agent A1500; the toughening agent can enhance the toughness of the wire, increase the storage time of the wire and reduce the brittle fracture of the polylactic resin caused by moisture absorption, has good compatibility with the thermo-reversible crosslinking composition and the flow modifier, can be fully plasticized in an extruder and ensures the stable quality of the wire.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant CA, antioxidant 1330, antioxidant 405, antioxidant 168, antioxidant 1035 and antioxidant 1098.
Preferably, the hydrolysis-resistant agent is an hydrolysis-resistant agent
1010. Hydrolysis resistant agent AS1, hydrolysis resistant agent AS4, hydrolysis resistant agent AS15, hydrolysis resistant agent Stabaxol P200, and hydrolysis resistant agentBio-SAHTM362 and an anti-hydrolysis agent TMP-2000.
Preferably, the method for preparing the thermoreversibly cross-linking composition comprises the following steps: under the condition of protective gas, mixing and stirring a furyl compound, a maleimide compound and a polymer compatilizer to obtain the thermoreversible crosslinking composition.
Preferably, the mass ratio of the furyl compound to the maleimide compound to the polymer compatilizer is 1-3: 1-2: 5-28.
Preferably, the furyl compound is a product obtained by performing addition reaction on 2-furaldehyde and a nitrogen-containing compound through amino and aldehyde according to an equivalent stoichiometric ratio (1:1), the temperature of the addition reaction is 60-90 ℃, and the time of the addition reaction is 3-4 hours.
Preferably, the nitrogen-containing compound is one or more of N, N' -diphenylethylenediamine, N-methylaniline, 1-methylpiperazine, 2-methylpiperazine, N-ethylpiperazine and 1-phenylpiperazine. The nitrogen-containing compound can eliminate the defect that the material performance is deteriorated due to high-temperature thermochemical reaction of an aldehyde group structure in a furfural structure in the melt extrusion process, simultaneously improve the molecular weight of the furan-based compound, and improve the bonding performance of the furan-based compound and the imide resin, so as to obtain the thermoreversible crosslinking composition with better heat resistance.
Preferably, the maleimide compound is one or two of N, N ' - (4,4 ' -methylenediphenyl) bismaleimide and N, N ' -m-phenylene bismaleimide.
Preferably, the N, N '- (4, 4' -methylenediphenyl) bismaleimide is one or more of D928, D930, D936 and D937 produced by Sichuan east Material science and technology group, Inc.
Preferably, the polymeric compatibilizer is a low viscosity compound containing an epoxy group, and functions to increase compatibility between the composition and the PLA resin.
Preferably, the polymer compatibilizer is one or more of neopentyl glycol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, glycerol tripropoxy triglycidyl ether, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl p-aminophenol, castor oil triglycidyl ether, ethylene glycol diglycidyl ether, allyl glycidyl ether, and 1, 2-cyclohexanedicarboxylic acid diglycidyl ester.
Preferably, in the preparation method of the thermoreversible crosslinking composition, the stirring speed is 500-800 r/min, and the stirring time is 10-20 min.
Preferably, in the preparation method of the thermoreversible crosslinking composition, the protective gas is a rare gas or nitrogen.
The preparation method of the polylactic acid 3D printing wire modified by the thermoreversible crosslinking composition comprises the following steps:
(1) drying polylactic acid, stirring, adding the thermoreversible crosslinking composition while stirring, and obtaining a material A after stirring;
(2) baking the material A, cooling to room temperature after baking to obtain a material B, mixing the fluidity modifier, the flexibilizer, the pigment, the antioxidant and the hydrolysis resistant agent with the material B, and stirring to uniformly mix the materials to obtain a material C;
(3) and extruding the material C by an extruder to obtain the thermoreversible crosslinking composition modified polylactic acid 3D printing wire.
Preferably, the drying temperature in the step (1) is 40-50 ℃, and the drying time is 8-12 h.
Preferably, the stirring speed in the step (1) is 200-500 r/min, and the stirring time is 10-20 min.
Preferably, the baking in the step (2) is vacuum baking, the baking temperature is 50-70 ℃, and the baking time is 2-4 hours.
Preferably, the stirring speed in the step (2) is 20-80 r/min, and the stirring time is 10-20 min.
Preferably, the extruder in the step (3) is a screw extruder with six temperature sections, and the extrusion temperature of each section of the extruder is 170-195 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the 3D printing wire prepared by modifying polylactic acid by adopting the thermoreversible crosslinking composition has smooth surface, stable wire diameter (1.75 +/-0.04 mm) and high thermal deformation temperature, the lowest tolerance temperature is 15-26 ℃ higher than that of the current general PLA, and the polylactic acid is favorably used for products with higher requirements on heat resistance.
(2) The material has high toughness, does not have brittle fracture of the wire after being placed for 3 months, and has simple preparation method and easy operation of steps;
(3) the material is high in fluidity in the 3D printing process, high in wire strength and good in glossiness, and can well meet the 3D printing requirement.
Drawings
FIG. 1 is an infrared spectrum of an adduct of N, N' -diphenylethylenediamine with 2-furaldehyde and 2-furaldehyde in example 1.
Fig. 2 is a diameter monitoring graph of the thermo-reversible cross-linking composition modified polylactic acid 3D printing wire in example 1.
Fig. 3 is a diameter monitoring diagram of the wire rod produced in reference example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
(1) Adding 9.6 g of 2-furaldehyde (an avastin reagent) and 21.2 g of N, N' -diphenylethylenediamine (an avastin reagent) into a reaction kettle under the condition of nitrogen, and reacting for 4 hours at 60 ℃; adding 61.6 g of N, N '- (4, 4' -methylenediphenyl) bismaleimide (D928, Sichuan Dong material science and technology group, Ltd.); 154 g of allyl glycidyl ether (Dongguan Yongzheng chemical Co., Ltd.) was added thereto and dispersed at a rotation speed of 500r/m for 10 minutes to obtain a thermoreversible crosslinking composition, and the infrared comparison of the adduct of 2-furaldehyde reacted with, N, N' -diphenylethylenediamine and 2-furaldehyde is shown in FIG. 1.
(2) Preparation of the thermoreversible cross-linked composition modified polylactic acid 3D printing wire: 1000 g of polylactic acid (Zhejiang Haizhen biological materials Co., Ltd., with the mark of PLA REVODE195) is put in an oven with the temperature of 50 ℃ to be dried for 8 hours; adding the mixture into a dispersion mixer, adding 180 g of the prepared thermoreversible crosslinking composition while stirring, and stirring for 20 minutes at the speed of 300 r/min; stopping stirring, and then baking the materials in the dispersion stirrer in a vacuum oven at 50 ℃ for 4 hours; after the temperature of the material is reduced to room temperature, the material is mixed with 6 g of flowability modifier YP-803 (Heizhou repulping chemical industry Co., Ltd.), 120 g of toughener YP-501 (Heizhou repulping chemical industry Co., Ltd.), 5 g of antioxidant 1330 and 16 g of hydrolysis resistant agent
1010 (Shanghai Langyi functional materials Co., Ltd.) was added to a mixer, and dispersed in a low-speed dispersion mixer at a mixing speed of 20r/min for 20 minutes; extruding in a single screw extruder under the following conditions: the temperature of each temperature zone of the extruder from the feed inlet to the discharge die was 180, 190, 185, 175 ℃ to give 1.75 ± 0.04mm white 3D printing wire, labeled as example 1. The properties of the devices after the wire was printed by the FDM method are shown in tables 1 and 2.
The same procedure as in example 1 was followed, except that the thermoreversible crosslinking composition was not added, and the other preparation steps were identical and are designated as reference 1.
The performances of the devices printed by FDM method at 205 ℃ of the 3D printing wires prepared in example 1 and reference 1 are shown in tables 1 and 2, and the diameter monitoring of the wires in example 1 and reference 1 is shown in fig. 2 and 3, which shows that the thermoreversible crosslinking composition does not have a great influence on the dimensional stability of the wires.
Example 2
(1) Adding 9.6 g of 2-furaldehyde (an avadin reagent) and 10.7 g of N-methylaniline (an avadin reagent) into a reaction kettle under the condition of nitrogen, and reacting for 3 hours at 60 ℃; adding 20.5 g of N, N '- (4, 4' -methylenediphenyl) bismaleimide (D930, Sichuan Dong material science and technology group, Ltd.); 122.5 g of 1, 2-cyclohexanedicarboxylic acid diglycidyl ester (New Material Co., Ltd. in Hubei province) was added and dispersed for 20 minutes at a rotation speed of 500r/m to obtain a thermoreversible crosslinking composition.
(2) Preparation of the thermoreversible cross-linked composition modified polylactic acid 3D printing wire: 1000 g of polylactic acid (PLA REVODE195-1, manufactured by Zhejiang Haizhen biomaterial Co., Ltd.) is dried in an oven at 60 ℃ for 6 hours; adding the mixture into a dispersion mixer, adding 150 g of the thermoreversible crosslinking composition while stirring, and stirring at the speed of 500r/min for 10 minutes; stopping stirring, and then baking the materials in the dispersion stirrer in a vacuum oven at 50 ℃ for 4 hours; after the temperature of the material is reduced to room temperature, the material is mixed with 6 g of a fluidity modifier FA700 (Basfu), 100 g of a toughening agent B308T (Shenzhen Pasteh New Material science and technology Co., Ltd.), 10 g of an antioxidant 1330, 1 g of iron oxide yellow (Guangzhou Langmen chemical industry Co., Ltd.) and 5 g of a hydrolysis resistant agent
1010 (Shanghai Langyi functional materials Co., Ltd.) was put into a rotating speed of 80r/min and mixed for 20 minutes, and extruded through a single screw extruder under the following conditions: the temperature of each temperature section of the extruder from the feeding hole to the direction of the discharging die is 185 ℃, 190 ℃, 195, 190 ℃ and 180 ℃ to obtain 1.75 +/-0.04 mm yellow 3D printing wires which are marked as example 2, and the performances of the devices after the wires are printed by the FDM method (the printing temperature is 200 ℃) are shown in tables 1 and 2.
The same procedure as in example 2 was followed, except that the thermoreversible crosslinking composition was not added, and the other preparation steps were identical and are designated as reference 2. The test properties of the molded devices after the wire was printed by the FDM method (printing temperature 200 ℃ C.) are shown in tables 1 and 2.
Example 3
(1) Adding 9.6 g of 2-furaldehyde (an avastin reagent) and 10 g of 2-methylpiperazine (an avastin reagent) into a reaction kettle under the condition of nitrogen, and reacting for 4 hours at 90 ℃; 6.6 g of N, N' -m-phenylenebismaleimide (Shanghai strontium Ming rubber & plastics science and technology Co., Ltd.) was added; 183.4 g of glycerol tripropoxy triglycidyl ether (Shenzhen, Virginian chemical Co., Ltd.) were added and dispersed at a rotation speed of 600r/min for 12 minutes to obtain a thermoreversible crosslinking composition.
(2) Preparation of the thermoreversible cross-linked composition modified polylactic acid 3D printing wire: 1000 g of polylactic acid reclaimed material (Zhejiang Haizhen biological material Co., Ltd., with the brand number of PLA REVODE195) is dried in an oven at the temperature of 50 ℃ for 8 hours; adding the mixture into a dispersion mixer, adding 80 g of the thermoreversible crosslinking composition while stirring, and stirring at the speed of 300r/min for 20 minutes; stopping stirring, and then baking the materials in the dispersion stirrer in a vacuum oven at 70 ℃ for 2 hours; after the temperature of the material is reduced to room temperature, the material is mixed with 30 g of a fluidity modifier YP-803 (Heizhou repulper chemical industry Co., Ltd.), 90 g of a toughener YP-501 (Heizhou repulper chemical industry Co., Ltd.), 2 g of iron oxide red (Fushan cyancin new material Co., Ltd.), 6 g of an antioxidant 405 and 16.5 g of a hydrolytic inhibitor Bio-SAHTM362 (Suzhou ke Sanotong new material science Co., Ltd.) in a low-speed dispersion mixer with the rotating speed of 80r/min for 15 minutes, and the mixture is extruded by a single-screw extruder, wherein the extrusion conditions are as follows: the temperature of each temperature zone of the extruder from the feed inlet to the discharge die was 175, 185, 190, 185, 170 ℃ to obtain a red 3D printed wire of 1.75 + -0.04 mm, which is labeled as example 3, and the properties of the device after the wire was printed by FDM (printing temperature 210 ℃) are shown in tables 1 and 2.
The same procedure as in example 3 was followed, except that the thermoreversible crosslinking composition was not added, and the other preparation steps were identical and are designated as reference 3. The properties of the device after the wire was printed by the FDM method (printing temperature 210 ℃ C.) are shown in tables 1 and 2.
Example 4
(1) Adding 9.6 g of 2-furaldehyde (an avastin reagent) and 16.2 g of 1-phenylpiperazine (an avastin reagent) into a reaction kettle under the condition of nitrogen, and reacting for 4 hours at 90 ℃; 15.6 g of N, N '- (4, 4' -methylenediphenyl) bismaleimide (D937, Sichuan Dong material science and technology group Co., Ltd.) were added; 165.6 g of cyclohexanedimethanol diglycidyl ether (Hexion Heloxy 107 reactive diluent, Vast Heloxy, Hexion) are added and dispersed for 15 minutes at a speed of 800r/min, giving a thermoreversible crosslinking composition.
(2) Preparation of the thermoreversible cross-linked composition modified polylactic acid 3D printing wire: 1000 g of polylactic acid reclaimed material (Zhejiang Haizhen biological material Co., Ltd., the mark PLA REVODE190) is put into an oven with the temperature of 50 ℃ to be dried for 12 hours; adding the mixture into a dispersion mixer, adding 120 g of the thermoreversible crosslinking composition while stirring, and stirring at the speed of 500r/min for 20 minutes; stopping stirring, and then baking the materials in the dispersion stirrer in a vacuum oven at 60 ℃ for 4 hours; after the temperature of the material was reduced to room temperature, the material was mixed with 30 g of flowability modifier YP-803 (hezhou repulping chemical corporation), 80 g of toughener a-869 (shenzhen golden encyclopedia limited company), 1 g of green pigment (8730 phthalo green, guangzhou Plumbum titanium white pigment), 8 g of antioxidant 1098 and 26.6 g of hydrolysis inhibitor TMP-2000 (hangzhou xi new metallocene technology limited company) in a low-speed dispersion mixer at a rotation speed of 80r/min for 20 minutes, extruded through a single-screw extruder, and extruded from a feed port to a discharge port at temperatures of 190, 200, 195, 190, 185 ℃ to obtain a green 3D printed wire of 1.75 ± 0.04mm, which is labeled as example 4, and the performances of the device after the wire was printed by the method are shown in tables 1 and 2.
The same procedure as in example 4 was followed, except that the thermoreversible crosslinking composition was not added, and the other preparation steps were identical and are designated as reference 4. The properties of the devices after the wire was printed by the FDM method are shown in tables 1 and 2.
The devices printed in examples 1 to 4 and reference examples 1 to 4 were dried and left at room temperature (25. + -. 2 ℃ C.) for 12 hours, and the test results are shown in Table 1.
TABLE 1 summary of the results of the performance tests of the samples of each example and reference example after 12 hours of storage
The devices printed in examples 1 to 4 and reference examples 1 to 4 were allowed to stand in a dry room temperature environment (25. + -. 2 ℃ C.) for 7 days, and then each performance was tested, and the test results are shown in Table 2.
TABLE 2 summary of the results of the performance tests of the samples of each example and reference example after 7 days of storage
From FIG. 1, it can be confirmed that the aldehyde group on the 2-furaldehyde completely reacts with the nitrogen-containing compound, i.e., the amino group is grafted into the 2-furyl compound.
As can be seen from Table 2, the heat resistance and the mechanical strength of the printed part of the polylactic acid 3D printing material modified by the thermoreversible crosslinking compound are correspondingly improved; and analyzing the thickness data of the wire rod, wherein the thickness of the wire rod is in a controllable range, and the condition that the thickness change of the wire rod exceeds the range does not occur.
Comparing table 1 and table 2, it is found that the melt index, wire diameter and other performance indexes of the unmodified PLA material are not changed, and the heat resistance and mechanical strength of the modified material are both obviously improved, which indicates that the thermoreversible crosslinked polymer is crosslinked into a crosslinked compound in the process of being placed at room temperature, and the heat resistance and mechanical strength of the product can be effectively improved.
Intercepting 10 meters of 3D printing wires obtained in examples 1-4, and observing with naked eyes under a light reflection condition, wherein no obvious bulge or dent is found (the line diameter stability represents the smoothness, and if the line diameter has a deviation of more than 0.1, the relevant surface bulge or dent can be seen), which indicates that the surface of the polylactic acid 3D printing material modified by the thermoreversible crosslinking compound prepared by the invention is smooth;
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. The 3D printing wire rod is characterized by comprising the following components in parts by mass:
100 parts of polylactic acid;
8-18 parts of a thermoreversible crosslinking composition;
0.6-4.5 parts of a fluidity modifier;
3-12 parts of a toughening agent;
0-5 parts of pigment;
0.5-1.2 parts of antioxidant;
0.5-3.2 parts of an anti-hydrolysis agent;
the preparation method of the thermoreversibly crosslinking composition comprises the following steps: under the condition of protective gas, mixing and stirring a furyl compound, a maleimide compound and a polymer compatilizer to obtain the thermoreversible crosslinking composition;
the furyl compound is a product obtained by performing addition reaction on 2-furaldehyde and a nitrogen-containing compound through amino and aldehyde according to the equivalent stoichiometric ratio (1:1), the temperature of the addition reaction is 60-90 ℃, and the time of the addition reaction is 3-4 hours; the nitrogen-containing compound is one or more than two of N, N' -diphenyl ethylenediamine, N-methylaniline, 1-methylpiperazine, 2-methylpiperazine, N-ethylpiperazine and 1-phenylpiperazine;
the polymer compatibilizer is a low viscosity compound containing an epoxy group.
2. The thermoreversibly crosslinkable composition-modified polylactic acid 3D printing wire according to claim 1, wherein the fluidity modifier is one or more of fluidity modifier YP-803, fluidity modifier FA-700, silicone powder 501, fluidity modifier FJ-100, fluidity modifier FJ-200, fluidity modifier FJ-300 and fluidity modifier FJ-400; the pigment is one or more than two of 100-400-mesh glitter powder, pearl powder, copper gold powder, iron oxide red, iron oxide yellow, phthalocyanine green, cobalt blue, iron chromium black and aluminum silver powder.
3. The thermoreversible crosslinking composition modified polylactic acid 3D printing wire of claim 2, wherein the toughening agent is one or two of toughening agent YF6030, toughening agent YP-501, toughening agent B308T, toughening agent a-869 and toughening agent a 1500; the antioxidant is one or more than two of antioxidant 1010, antioxidant CA, antioxidant 1330, antioxidant 405, antioxidant 168, antioxidant 1035 and antioxidant 1098; the hydrolysis resistant agent is one of hydrolysis resistant agent HyMax 1010, hydrolysis resistant agent AS1, hydrolysis resistant agent AS4, hydrolysis resistant agent AS15, hydrolysis resistant agent Stabaxol P200, hydrolysis resistant agent Bio-SAH trap 362 and hydrolysis resistant agent TMP-2000.
4. The 3D printing wire rod of the thermoreversibly cross-linked composition modified polylactic acid as claimed in claim 1, wherein the mass ratio of the furyl compound, the maleimide compound and the polymer compatilizer is 1-3: 1-2: 5-28.
5. The thermoreversibly crosslinkable composition-modified polylactic acid 3D printing wire according to claim 3, wherein said maleimide-based compound is one or both of N, N ' - (4,4 ' -methylenediphenyl) bismaleimide and N, N ' -m-phenylenebismaleimide; the protective gas is rare gas or nitrogen.
6. The preparation method of the thermoreversible crosslinking composition modified polylactic acid 3D printing wire rod according to any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) drying polylactic acid, stirring, adding the thermoreversible crosslinking composition while stirring, and obtaining a material A after stirring;
(2) baking the material A, cooling to room temperature after baking to obtain a material B, mixing the fluidity modifier, the flexibilizer, the pigment, the antioxidant and the hydrolysis resistant agent with the material B, and stirring to uniformly mix the materials to obtain a material C;
(3) and extruding the material C by an extruder to obtain the thermoreversible crosslinking composition modified polylactic acid 3D printing wire.
7. The preparation method of the 3D printing wire rod modified by the thermoreversible crosslinking composition according to claim 6, wherein the drying temperature in the step (1) is 40-50 ℃, and the drying time is 8-12 h; the stirring speed of the step (1) is 200-500 r/min, and the stirring time is 10-20 min.
8. The preparation method of the 3D printing wire rod modified by the thermoreversible crosslinking composition according to claim 6, wherein the baking in the step (2) is vacuum baking, the baking temperature is 50-70 ℃, and the baking time is 2-4 h; the stirring speed of the step (2) is 20-80 r/min, and the stirring time is 10-20 min; and (3) the extruder is a screw extruder with six temperature sections, and the extrusion temperature of each section of the extruder is 170-195 ℃.
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