Preparation method and application of poly (butylene succinate) 3D printing wire

Abstract

The invention belongs to the technical field of 3D printing material preparation, and discloses a preparation method and application of a poly (butylene succinate) 3D printing wire rod, and the preparation method comprises the following steps: sequentially carrying out esterification and condensation polymerization on butanediol, succinic acid, a heterocyclic compound, a multi-arm branching agent and an auxiliary agent to obtain poly (butylene succinate) copolyester; carrying out melt extrusion on the poly (butylene succinate) copolyester to obtain a poly (butylene succinate) 3D printing wire; the heterocyclic compound is heterocyclic diol or heterocyclic diacid. Through structural composition design of a polymer, an esterification modification technology of poly (butylene succinate) is adopted, and a heterocycle modified functional group and a multi-arm monomer are added, modified and compounded, and a printing process is regulated and controlled, so that development of a 3D printing material of PBS is realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of 3D printing material preparation, and relates to a preparation method and application of polybutylene succinate 3D printing wire. Background Art

[0002] 3D printing technology, also known as "additive manufacturing," is a method of creating physical objects by printing layers of adhesive materials under computer program control. Compared to traditional molding processes, 3D printing offers the following advantages: It eliminates the need for traditional production machine tools and expensive molds, directly converting 3D CAD models into 3D solids, significantly reducing product development and production time. It eliminates the need for waste material, significantly increasing material utilization and reducing costs. It can also produce highly complex components that are difficult to manufacture with traditional techniques, particularly those with complex hollow structures, thereby achieving lightweight products.

[0003] While 3D printing technology has made rapid progress in recent years, research into printing consumables has lagged behind, and the range of materials available remains limited. In particular, the selection of printing consumables in fused deposition modeling (FDM) technology is crucial for expanding the application of 3D printing technology.

[0004] FDM molding technology primarily relies on thermoplastics or low-melting-point metal filaments as printing materials. These materials must possess specific properties, such as a suitable melting temperature range, a suitable melt flow rate (MFR), and low shrinkage. Currently, commonly used materials in FDM molding technology include acrylonitrile-butadiene-styrene copolymer (ABS), polylactic acid (PLA), polycarbonate (PC), nylon (PA), polyvinyl alcohol (PVA), thermoplastic polyurethane (TPU), and polyetheretherketone (PEEK). From the perspective of material degradability, traditional FDM materials can be roughly divided into two categories: non-degradable materials, represented by ABS, and biodegradable materials, represented by PLA. ABS and PLA have the most extensive applications. However, the softening point of PLA is only 65°C, which to some extent limits its scope of use.

[0005] In search of more promising biodegradable materials, polybutylene succinate (PBS) has come into focus. PBS has a melting temperature of 115°C, which meets the requirements of low-temperature processing, and its softening point is close to 100°C, which has greater application potential compared to PLA's 65°C. However, as an aliphatic polyester, PBS has low melt strength, is highly sensitive to temperature, and has a narrow processing window. In addition, the high crystallinity of PBS polymers leads to high residual stress in the material, making it prone to warping during printing.

[0006] To overcome these challenges, existing technologies are constantly seeking solutions. For example, patent application CN105255122A discloses a polybutylene succinate (PBS) 3D printing filament and its preparation method. By adding a nucleating agent, the size of the PBS spherulites can be regulated, and the crystallization behavior of the PBS can be controlled to achieve processing. However, the addition of the nucleating agent can lead to uneven distribution and phase separation of the material.

[0007] Patent application with publication number CN108727571A discloses a modified polyester 3D printing material based on PBS, its preparation method and application. The material is prepared by copolymerizing and adding a third monomer to reduce the crystallinity and processing fluidity of PBS. However, the heat resistance of the material prepared by this method is also significantly reduced, and the original heat resistance advantage of the polymer cannot be retained.

[0008] Therefore, a preparation method and application of polybutylene succinate 3D printing filament are needed to solve the above problems, which is of great significance. Summary of the Invention

[0009] The purpose of the present invention is to solve the problems existing in the prior art and provide a preparation method and application of polybutylene succinate 3D printing wire.

[0010] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0011] A method for preparing polybutylene succinate 3D printing filament comprises sequentially subjecting butanediol, succinic acid, a heterocyclic compound, a multi-arm branching agent, and an additive to esterification and polycondensation to obtain polybutylene succinate copolyester, and then melt-extruding the polybutylene succinate copolyester to obtain the polybutylene succinate 3D printing filament;

[0012] The heterocyclic compound is a heterocyclic diol or a heterocyclic diacid.

[0013] FDM 3D printing is a method of printing by depositing molten polymer layer by layer. Figure 1 As shown, the printed samples are stacked layer by layer in this way, so the interlayer cracks between the layers will affect the mechanical properties of the polymer, causing it to peel and break during use. PBS itself is a highly crystalline polymer with a relatively fast crystallization rate, resulting in insufficient adhesion between the polymer layers and prone to mechanical defects. To this end, the present invention uses a rigid heterocyclic structure to copolymerize the polymer to reduce the crystallization rate, ultimately achieving tight adhesion between the layers.

[0014] PBS is an aliphatic polyester with low melt strength, high temperature sensitivity, and a narrow processing window. Simultaneously, PBS polymers have high crystallinity, resulting in high residual stress in the material, making it prone to warping during printing. The present invention uses a multi-arm branching agent to modify the chemical structure, forming molecular entanglement points, reducing the fluidity of the polymer and broadening the processing window. Furthermore, the introduction of the multi-arm branching agent can, to a certain extent, disrupt the regularity of the polymer itself, reducing the crystallinity of the polymer material and the residual stress of the finished product, making warping less likely to occur.

[0015] As the preferred technical solution:

[0016] In the above-mentioned method for preparing a polybutylene succinate 3D printing filament, the heterocyclic diol is isosorbide, isomannide, furandimethanol or tetrahydrofuran dimethanol, and the heterocyclic diacid is furandicarboxylic acid.

[0017] In the above-mentioned method for preparing a polybutylene succinate 3D printing filament, the multi-arm branching agent is one or more of glycerol, trimethylolpropane, pentaerythritol and castor oil.

[0018] The method for preparing a polybutylene succinate 3D printing filament as described above, wherein when the heterocyclic compound is a heterocyclic diol, the molar ratio of the total amount of butanediol and the heterocyclic compound to succinic acid is 1.15-1.25:1, and the molar percentage of the heterocyclic compound to the total amount of butanediol and the heterocyclic compound is 10-20%;

[0019] When the heterocyclic compound is a heterocyclic diacid, the molar ratio of butanediol to the total amount of succinic acid and the heterocyclic compound is 1.15 to 1.25:1, and the molar percentage of the heterocyclic compound to the total amount of succinic acid and the heterocyclic compound is 10 to 20%;

[0020] The molar percentage of the multi-arm branching agent to the succinic acid is 0.1 to 3%.

[0021] In the above-mentioned method for preparing a polybutylene succinate 3D printing filament, the auxiliary agents include a catalyst, an antioxidant and a thermal stabilizer.

[0022] In the method for preparing polybutylene succinate 3D printing filament as described above, the catalyst is tetrabutyl titanate and / or antimony butanediol, and the catalyst dosage is 0.05-0.20% by mass of succinic acid; the antioxidant dosage is 0.05-0.20% by mass of succinic acid; and the thermal stabilizer is triphenyl phosphite, and the thermal stabilizer dosage is 0.05-0.20% by mass of succinic acid.

[0023] In the method for preparing the polybutylene succinate 3D printing filament as described above, the esterification temperature is 170-200° C., the esterification time is 3-5 hours, and the polycondensation temperature is 220-250° C., and the polycondensation time is 3-6 hours.

[0024] In the method for preparing the polybutylene succinate 3D printing filament as described above, the intrinsic viscosity of the polybutylene succinate copolyester is 0.9 to 1.3 dL / g.

[0025] According to the method for preparing a polybutylene succinate 3D printing filament as described above, the diameter of the polybutylene succinate 3D printing filament is 1.75±0.05 mm.

[0026] Beneficial effects:

[0027] (1) The present invention reduces the crystallization rate of the polymer by copolymerizing with a rigid heterocyclic structure, thereby ultimately achieving close bonding between layers during 3D printing.

[0028] (2) The present invention adopts a multi-arm branching agent and chemical structure modification to form molecular entanglement points, reduce the fluidity of the polymer, broaden the processing window, and achieve 3D printing without melt breakage due to excessive melt elasticity; at the same time, the introduction of the multi-arm branching agent can destroy the regularity of the polymer itself to a certain extent, reduce the crystallinity of the polymer material, reduce the residual stress of the finished product, and is less likely to cause warping problems.

[0029] (3) In order to avoid the influence of copolymerization on processing, the present invention adopts a multi-arm branching agent to achieve the regulation of melt strength, and adopts a rigid heterocyclic structure to increase the rigidity of the polymer chain. Since the glass transition temperature is a macroscopic manifestation of the flexibility of the polymer chain, for amorphous polymers, increasing the rigidity of the molecular chain will increase its glass transition temperature; for crystalline polymers, increasing the rigidity of the molecular chain will increase the melting point temperature. Therefore, the present invention avoids the reduction of the heat resistance of polybutylene succinate 3D printing wire.

[0030] (4) The present invention adopts a melt branching preparation route, one-step molding, and the preparation method is simple and the reaction conditions are mild. At the same time, the raw materials are widely available, have good compatibility, are non-toxic and harmless, and are inexpensive, making them suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a schematic diagram of the printing process using a layer-by-layer deposition method of molten polymer in the present invention;

[0032] Figure 2 This is an SEM image of the upper layer and the superposition of the layers on the side of the spline printed in Example 5. DETAILED DESCRIPTION

[0033] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0034] In order to ensure that the properties of the materials used in each embodiment and comparative example are fully disclosed, the manufacturers and brands of the materials are indicated. Products of other manufacturers and brands that meet the requirements of the present invention are also feasible.

[0035] The testing methods for the relevant performance indicators in the following embodiments and comparative examples are as follows:

[0036] Glass transition temperature, melting point, melting enthalpy, crystallization enthalpy, and crystallization temperature: The polybutylene succinate 3D printing filaments prepared in each example were used as samples, and then the glass transition temperature, melting point, melting enthalpy, crystallization enthalpy, and crystallization temperature of the samples were tested with reference to GB / T 19466.3-2004: "Plastics Differential Scanning Calorimetry (DSC) Part 3: Determination of Melting and Crystallization Temperatures and Enthalpy" standard.

[0037] Intrinsic viscosity: The polybutylene succinate copolyester obtained in each example was used as a sample, and then the intrinsic viscosity of the sample was tested using an Ubbelohde viscometer at 25°C, referring to Method A in GB / T14190-2017 "Test Method for Fiber-Grade Polyester Chips (PET)". The mixed solvent used in the test was a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (1:1 w / w) with a mass ratio of 50:50. The concentration of the sample and the mixed solvent after mixing was 0.50 g·dL -1 .

[0038] Tensile strength: The specimens prepared in each embodiment were used as samples, and then the tensile strength of the samples was tested with reference to GB / T 1040-2018 "Determination of tensile properties of plastics".

[0039] Example 1

[0040] A method for preparing polybutylene succinate 3D printing filament, comprising the following steps:

[0041] (1) Under the protection of nitrogen, butanediol, succinic acid, isosorbide, glycerol, tetrabutyl titanate, antioxidant 1010 and triphenyl phosphite are subjected to an esterification reaction at normal pressure, and then a polycondensation reaction is carried out at a vacuum degree of 30 Pa to obtain polybutylene succinate copolyester; wherein the molar ratio of the total molar amount of butanediol and isosorbide to succinic acid is 1.15:1, the molar percentage of isosorbide in the total molar amount of butanediol and isosorbide is 15%, the molar percentage of glycerol in the succinic acid is 3%, the amount of tetrabutyl titanate is 0.1% of the mass of the succinic acid, the amount of antioxidant 1010 is 0.1% of the mass of the succinic acid, and the amount of triphenyl phosphite is 0.1% of the mass of the succinic acid; the esterification temperature is 170°C, the esterification time is 3 hours; the polycondensation temperature is 220°C, and the polycondensation time is 3 hours;

[0042] The intrinsic viscosity of polybutylene succinate copolyester is 0.9 dL / g;

[0043] (2) Polybutylene succinate copolyester is melt-extruded to obtain polybutylene succinate 3D printing filament.

[0044] The diameter of the polybutylene succinate 3D printing filament prepared is 1.70 mm, the glass transition temperature is -20.1 ° C, the melting point is 95.7 ° C, and the melting enthalpy is 62.5 J·g -1 , the crystallization temperature is 45.5℃, and the crystallization enthalpy is 30.4J·g -1 ;

[0045] The FDM technology was used to print dumbbell-shaped splines (size 75mm×10mm×2mm) of polybutylene succinate 3D printing filament at a printing temperature of 125°C and a heating plate of 55°C. The tensile strength of the spline was 32.2MPa.

[0046] Example 2

[0047] A method for preparing polybutylene succinate 3D printing filament, comprising the following steps:

[0048] (1) Under the protection of nitrogen, butanediol, succinic acid, isomannose, pentaerythritol, antimony butanediol, antioxidant 1010 and triphenyl phosphite are subjected to an esterification reaction at normal pressure, and then a polycondensation reaction is carried out at a vacuum degree of 40 Pa to obtain polybutylene succinate copolyester; wherein the molar ratio of the total molar amount of butanediol and isomannose to succinic acid is 1.2:1, the molar percentage of isomannose to the total molar amount of butanediol and isomannose is 10%, the molar percentage of pentaerythritol to the succinic acid is 2%, the amount of antimony butanediol is 0.1% by mass of the succinic acid, the amount of antioxidant 1010 is 0.1% by mass of the succinic acid, and the amount of triphenyl phosphite is 0.1% by mass of the succinic acid; the esterification temperature is 185° C., the esterification time is 4 h; the polycondensation temperature is 230° C., and the polycondensation time is 4 h;

[0049] The intrinsic viscosity of polybutylene succinate copolyester is 1 dL / g;

[0050] (2) Polybutylene succinate copolyester is melt-extruded to obtain polybutylene succinate 3D printing filament.

[0051] The diameter of the prepared polybutylene succinate 3D printing filament is 1.77 mm, the glass transition temperature is -18.7 ° C, the melting point is 103.2 ° C, and the melting enthalpy is 59.2 J·g -1 The crystallization temperature is 53.1℃ and the crystallization enthalpy is 56.9J·g -1 ;

[0052] The FDM technology was used to print dumbbell-shaped splines (size 75mm×10mm×2mm) of polybutylene succinate 3D printing filament at a printing temperature of 130°C and a heating plate of 60°C. The tensile strength of the spline was 35.7MPa.

[0053] Example 3

[0054] A method for preparing polybutylene succinate 3D printing filament, comprising the following steps:

[0055] (1) Under the protection of nitrogen, butanediol, succinic acid, furandimethanol, castor oil, tetrabutyl titanate and antimony butanediol in a mass ratio of 1:1, antioxidant 1010 and triphenyl phosphite are subjected to esterification reaction at normal pressure, and then polycondensation reaction is carried out at a vacuum degree of 50 Pa to obtain polybutylene succinate copolyester; wherein the molar ratio of the total amount of butanediol and furandimethanol to succinic acid is 1.2:1, and the molar ratio of furandimethanol to butanediol is 1:1. The molar percentage of the total molar amount of alcohol and furandimethanol is 15%, the molar percentage of castor oil in succinic acid is 0.5%, the amount of tetrabutyl titanate and antimony butanediol is 0.1% by mass of the succinic acid, the amount of antioxidant 1010 is 0.1% by mass of the succinic acid, and the amount of triphenyl phosphite is 0.1% by mass of the succinic acid; the esterification temperature is 200° C., the esterification time is 5 hours; the polycondensation temperature is 250° C., and the polycondensation time is 6 hours;

[0056] The intrinsic viscosity of polybutylene succinate copolyester is 1.3 dL / g;

[0057] (2) Polybutylene succinate copolyester is melt-extruded to obtain polybutylene succinate 3D printing filament.

[0058] The diameter of the prepared polybutylene succinate 3D printing filament is 1.80 mm, the glass transition temperature is -28.7 ° C, the melting point is 100.4 ° C, and the melting enthalpy is 54.3 J·g -1 , the crystallization temperature is 34.6℃, and the crystallization enthalpy is 45.8J·g-1 ;

[0059] The FDM technology was used to print dumbbell-shaped splines (size 75mm×10mm×2mm) of polybutylene succinate 3D printing filament at a printing temperature of 135°C and a heating plate of 45°C. The tensile strength of the spline was 45.5MPa.

[0060] Example 4

[0061] A method for preparing polybutylene succinate 3D printing filament, comprising the following steps:

[0062] (1) Under the protection of nitrogen, butanediol, succinic acid, furandicarboxylic acid, glycerol and pentaerythritol in a mass ratio of 1:1, tetrabutyl titanate, antioxidant 1010 and triphenyl phosphite are subjected to an esterification reaction at normal pressure, and then a polycondensation reaction is carried out at a vacuum degree of 35 Pa to obtain polybutylene succinate copolyester; wherein the molar ratio of butanediol to the total molar amount of succinic acid and furandicarboxylic acid is 1.25:1, furandicarboxylic acid accounts for 20% of the total molar amount of succinic acid and furandicarboxylic acid, the total amount of glycerol and pentaerythritol accounts for 1% of the molar percentage of succinic acid, the amount of tetrabutyl titanate is 0.1% of the mass of succinic acid, the amount of antioxidant 1010 is 0.1% of the mass of succinic acid, and the amount of triphenyl phosphite is 0.1% of the mass of succinic acid; the esterification temperature is 190°C, the esterification time is 4 hours, the polycondensation temperature is 230°C, and the polycondensation time is 4 hours;

[0063] The intrinsic viscosity of polybutylene succinate copolyester is 1.1 dL / g;

[0064] (2) Polybutylene succinate copolyester is melt-extruded to obtain polybutylene succinate 3D printing filament.

[0065] The diameter of the polybutylene succinate 3D printing filament prepared is 1.73 mm, the glass transition temperature is -23.1 ° C, the melting point is 93.1 ° C, and the melting enthalpy is 60.8 J·g -1 The crystallization temperature is 25.9℃ and the crystallization enthalpy is 15.4J·g -1 ;

[0066] FDM technology was used to print dumbbell-shaped splines (size 75mm×10mm×2mm) of polybutylene succinate 3D printing filament at a printing temperature of 120°C and a heating plate of 35°C. The tensile strength of the spline was 27.3MPa.

[0067] Example 5

[0068] A method for preparing polybutylene succinate 3D printing filament, comprising the following steps:

[0069] (1) Under the protection of nitrogen, butanediol, succinic acid, isosorbide, pentaerythritol, tetrabutyl titanate and antimony butanediol in a mass ratio of 1:1, antioxidant 1010 and triphenyl phosphite are subjected to esterification reaction at normal pressure, and then polycondensation reaction is carried out at a vacuum degree of 40 Pa to obtain polybutylene succinate copolyester; wherein the molar ratio of the total amount of butanediol and isosorbide to the molar ratio of succinic acid is 1.2:1, and isosorbide accounts for 1% of butanediol. The molar percentage of the total molar amount of isosorbide is 10%, the molar percentage of pentaerythritol in succinic acid is 1.5%, the amount of tetrabutyl titanate and antimony butanediol is 0.1% by mass of the succinic acid, the amount of antioxidant 1010 is 0.1% by mass of the succinic acid, and the amount of triphenyl phosphite is 0.1% by mass of the succinic acid; the esterification temperature is 195° C., the esterification time is 4 hours; the polycondensation temperature is 240° C., and the polycondensation time is 5 hours;

[0070] The intrinsic viscosity of polybutylene succinate copolyester is 1.2 dL / g;

[0071] (2) Polybutylene succinate copolyester is melt-extruded to obtain polybutylene succinate 3D printing filament.

[0072] The diameter of the polybutylene succinate 3D printing filament prepared is 1.75 mm, the glass transition temperature is -24.6 ° C, the melting point is 106.3 ° C, and the melting enthalpy is 72.7 J·g -1 The crystallization temperature is 57.4℃ and the crystallization enthalpy is 54.8J·g -1 ;

[0073] The FDM technology was used to print the dumbbell-shaped spline (the side of the spline is as shown in the figure) with polybutylene succinate 3D printing filament at a printing temperature of 145°C and a heating plate of 65°C. Figure 2 As shown in the figure, it can be seen that the bonding between the layers is tight) (the size is 75mm×10mm×2mm), and the tensile strength of the spline is 42.4MPa.

[0074] Example 6

[0075] A method for preparing polybutylene succinate 3D printing filament, comprising the following steps:

[0076] (1) Under the protection of nitrogen, butanediol, succinic acid, tetrahydrofuran dimethanol, trimethylolpropane, tetrabutyl titanate, antioxidant 1010 and triphenyl phosphite are subjected to an esterification reaction at normal pressure, and then a polycondensation reaction is carried out at a vacuum degree of 55 Pa to obtain polybutylene succinate copolyester; wherein the molar ratio of the total molar amount of butanediol and tetrahydrofuran dimethanol to succinic acid is 1.2:1, the molar percentage of tetrahydrofuran dimethanol in the total molar amount of butanediol and tetrahydrofuran dimethanol is 10%, the molar percentage of trimethylolpropane in the succinic acid is 1%, the amount of tetrabutyl titanate is 0.1% of the mass of succinic acid, the amount of antioxidant 1010 is 0.1% of the mass of succinic acid, and the amount of triphenyl phosphite is 0.1% of the mass of succinic acid; the esterification temperature is 200°C, the esterification time is 4 hours, the polycondensation temperature is 240°C, and the polycondensation time is 4 hours;

[0077] The intrinsic viscosity of polybutylene succinate copolyester is 1.15 dL / g;

[0078] (2) Polybutylene succinate copolyester is melt-extruded to obtain polybutylene succinate 3D printing filament.

[0079] The diameter of the polybutylene succinate 3D printing filament prepared is 1.73 mm, the glass transition temperature is -27.3 ° C, the melting point is 103.4 ° C, and the melting enthalpy is 46.2 J·g -1 , the crystallization temperature is 41.3℃, and the crystallization enthalpy is 42.1J·g -1 ;

[0080] FDM technology was used to print dumbbell-shaped splines (size 75mm×10mm×2mm) of polybutylene succinate 3D printing filament at a printing temperature of 135°C and a heating plate of 50°C. The tensile strength of the spline was 28.6MPa.

Claims

1. A method for preparing polybutylene succinate 3D printing wire, characterized in that: Butanediol, succinic acid, a heterocyclic compound, a multi-arm branching agent and an additive are sequentially subjected to esterification and polycondensation to obtain polybutylene succinate copolyester, and the polybutylene succinate copolyester is melt-extruded to obtain polybutylene succinate 3D printing filament; The heterocyclic compound is a heterocyclic diol or a heterocyclic diacid.

2. The method for preparing a polybutylene succinate 3D printing wire according to claim 1, wherein: The heterocyclic diol is isosorbide, isomannide, furandimethanol or tetrahydrofurandimethanol, and the heterocyclic diacid is furandicarboxylic acid.

3. The method for preparing a polybutylene succinate 3D printing wire according to claim 1, wherein: The multi-arm branching agent is one or more of glycerol, trimethylolpropane, pentaerythritol and castor oil.

4. The method for preparing a polybutylene succinate 3D printing wire according to claim 3, wherein: When the heterocyclic compound is a heterocyclic diol, the molar ratio of the total amount of butanediol and the heterocyclic compound to succinic acid is 1.15 to 1.25:1, and the molar percentage of the heterocyclic compound to the total amount of butanediol and the heterocyclic compound is 10 to 20%; When the heterocyclic compound is a heterocyclic diacid, the molar ratio of butanediol to the total amount of succinic acid and the heterocyclic compound is 1.15 to 1.25:1, and the molar percentage of the heterocyclic compound to the total amount of succinic acid and the heterocyclic compound is 10 to 20%; The molar percentage of the multi-arm branching agent to the succinic acid is 0.1 to 3%.

5. The method for preparing a polybutylene succinate 3D printing wire according to claim 1, wherein: Additives include catalysts, antioxidants and thermal stabilizers.

6. The method for preparing a polybutylene succinate 3D printing wire according to claim 5, characterized in that: The catalyst is tetrabutyl titanate and / or antimony butanediol, and the amount of the catalyst is 0.05-0.20% by mass of the succinic acid; the antioxidant is antioxidant 1010, and the amount of the antioxidant is 0.05-0.20% by mass of the succinic acid; the heat stabilizer is triphenyl phosphite, and the amount of the heat stabilizer is 0.05-0.20% by mass of the succinic acid.

7. The method for preparing a polybutylene succinate 3D printing wire according to claim 1, characterized in that: The esterification temperature is 170-200°C, and the esterification time is 3-5 hours; the polycondensation temperature is 220-250°C, and the polycondensation time is 3-6 hours.

8. The method for preparing a polybutylene succinate 3D printing wire according to claim 1, wherein: The intrinsic viscosity of polybutylene succinate copolyester is 0.9 to 1.3 dL / g.

9. The method for preparing a polybutylene succinate 3D printing wire according to claim 1, wherein: The diameter of polybutylene succinate 3D printing filament is 1.75±0.05mm.

10. Application of the polybutylene succinate 3D printing filament prepared by the preparation method according to any one of claims 1 to 9, characterized in that: Used to use FDM technology for 3D printing to obtain printed products.

Images