CN116003980A - Polylactic acid 3D printing material with heat resistance, high strength and stable size and preparation method thereof - Google Patents
Polylactic acid 3D printing material with heat resistance, high strength and stable size and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and discloses a heat-resistant high-strength dimensionally stable polylactic acid 3D printing material and a preparation method thereof. The heat-resistant high-strength dimensionally stable polylactic acid 3D printing material comprises: polylactic acid, negative expansion filler, hyperbranched polyester, dibasic ester, catalyst, nucleating agent, lubricant, antioxidant and anti-hydrolysis agent. The material compensates the shrinkage caused by polylactic acid crystallization by utilizing the characteristic of cooling expansion of the negative thermal expansion filler, thereby avoiding the shrinkage deformation of the printing product. In addition, the hyperbranched polyester is grafted on the surface of the negative thermal expansion filler, so that the dispersion degree of the negative thermal expansion filler in the polylactic acid and the interface strength of the polylactic acid matrix and the filler are effectively improved; the processing flow property of the polylactic acid filling system is obviously improved, so that the bonding strength between extruded material strips in the 3D printing and forming process is effectively improved, the mechanical strength of the product is further improved, and the polylactic acid 3D printing product with heat resistance, high strength and stable size is prepared.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polylactic acid 3D printing material with heat resistance, high strength and stable size and a preparation method thereof.
Background
The 3D printing technology has been widely used in biomedical applications, toys, ornaments, material molding processes, and the like. Fused Deposition Modeling (FDM) is a 3D printing molding technology invented by Scott Crump in 1988, and the method comprises the steps of heating and fusing thermoplastic wires, extruding the thermoplastic wires from a nozzle of a printer, and stacking and accumulating extruded melt on a substrate layer by layer under the control of a path program set by software, so as to finally prepare the 3D printing product. Compared with other 3D printing technologies, the FDM technology has the characteristics of simplicity in operation, low material cost, high reliability, clean working environment and the like, is widely welcome by people, and is one of the most widely applied 3D printing technologies.
Currently, common polymeric materials for FDM molding mainly include acrylonitrile-butadiene-styrene copolymer (ABS), polyamide (PA), polylactic acid (PLA), and the like. The PLA is used as a degradable polymer material, and is one of the most popular 3D printing materials at present due to the advantages of low printing temperature, no toxic or harmful gas generation during printing and the like. However, the low heat resistance temperature (< 60 ℃) of the products obtained by PLA printing at present makes the products difficult to be applied to the field with high requirements on heat resistance, which greatly limits the application of PLA in 3D printing materials.
For PLA, methods for improving its heat resistance mainly include methods of filling modification, blending with a high heat resistant polymer, improving crystallinity, and the like. Among these, the improvement of crystallinity can improve the heat resistance thereof to the maximum extent without changing the degradability of PLA, and is therefore a heat-resistant modification method of highest application valueOne of the methods. However, since PLA undergoes significant shrinkage after crystallization (in terms of the densities of amorphous PLA and crystalline PLA (1.245 g/cm, respectively) 3 And 1.270g/cm 3 ) By calculation, the crystallization shrinkage rate can reach 2.0 percent, so that the crystallization modified PLA can generate extremely high internal stress between layers due to crystallization shrinkage in the 3D printing process, which not only can seriously reduce the bonding strength between the layers, but also can cause obvious deformation of a 3D printed product, and therefore, a high heat-resistant product with high mechanical property and stable size cannot be obtained.
Aiming at the problem of large crystallization shrinkage of the polymer, the filling modification of the polymer by using inorganic fillers (silicon dioxide, talcum powder, calcium carbonate and the like) is the most common method. The addition of the inorganic filler reduces the content of the polymer which can undergo crystallization shrinkage due to its low thermal expansion coefficient, and thus can exert an effect of reducing crystallization shrinkage of the polymer. When the inorganic filler content is low (< 20%), the reduction in the crystallization shrinkage is very limited, and only when the inorganic filler content is high (> 30%), the effect is more remarkable. However, when the filler content is high, this leads to a significant increase in the viscosity of the polymer, and for a fused deposited 3D printing material, on the one hand, too high a wire viscosity tends to cause clogging of the melt extrusion nozzle, resulting in difficulty in printing; on the other hand, the material strips with higher viscosity have small contact area after melt extrusion, are difficult to infiltrate each other, so that the bonding strength between the material strips is low, and the internal void defects of the product are more; in addition, high levels of filler are difficult to uniformly disperse in the polymer matrix and are prone to agglomeration, so that the final product has very low mechanical strength. Therefore, a great challenge still exists in preparing polylactic acid 3D printing materials with heat resistance, high strength and stable size.
Disclosure of Invention
The invention aims to overcome the defects of the background technology, and provides a heat-resistant high-strength and dimensionally stable polylactic acid 3D printing material, which compensates crystallization shrinkage caused by crystallization of polylactic acid by utilizing the characteristic of cooling expansion of a negative thermal expansion filler, remarkably reduces internal stress of the crystallization modified polylactic acid between layers in the 3D printing process, avoids shrinkage deformation of a printed product, is beneficial to improving adhesion between extruded strips, and can effectively improve the mechanical property of the product while remarkably improving the 3D printing processability of the polylactic acid. In addition, the hyperbranched polyester is grafted on the surface of the negative thermal expansion filler, so that the dispersion degree of the negative thermal expansion filler in the polylactic acid and the interface strength of a polylactic acid matrix and the filler are effectively improved, the processing flow property of a polylactic acid filling system is effectively improved, and finally the polylactic acid 3D printing material with heat resistance, high strength and stable size is prepared.
In order to achieve the purpose of the invention, the heat-resistant high-strength dimensionally stable polylactic acid 3D printing material comprises the following components in parts by mass:
polylactic acid: 100 parts of
Negative expansion filler: 15-30 parts
Hyperbranched polyesters: 1 to 8 parts of
Dibasic ester: 0.5 to 2 parts
Catalyst: 0.05 to 0.2 part
Nucleating agent: 0.1 to 3 parts
And (3) a lubricant: 0.1 to 0.5 part
An antioxidant: 0.1 to 0.5 part
Hydrolysis inhibitor: 0.1 to 1 part.
Preferably, in some embodiments of the present invention, the heat-resistant high-strength dimensionally stable polylactic acid 3D printing material includes the following components in parts by mass:
polylactic acid: 100 parts of
Negative expansion filler: 25-30 parts
Hyperbranched polyesters: 5-8 parts
Dibasic ester: 1.5 to 2 parts
Catalyst: 0.15 to 0.2 part
Nucleating agent: 0.5 to 2 parts
And (3) a lubricant: 0.3 to 0.5 part
An antioxidant: 0.3 to 0.5 part
Hydrolysis inhibitor: 0.8 to 1 part.
Further, in some embodiments of the present invention, the polylactic acid has an optical purity of 95% or more and a melt index of 5 to 20g/10min (190 ℃,2.16 kg).
Further, in some embodiments of the invention, the negative expansion filler is one or both of zinc pyrophosphate and copper pyrophosphate.
Further, in some embodiments of the invention, the hyperbranched polyester is one or more of hyperbranched resins hypec 100, hypec 181, hypec 182.
Further, in some embodiments of the invention, the dibasic ester is one or more of dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate.
Further, in some embodiments of the invention, the catalyst is one or more of tetrapropyl titanate, tetrabutyl titanate, and toluene sulfonic acid.
Further, in some embodiments of the invention, the nucleating agent is one or more of zinc phenylphosphate, diphenyldihydrazide sebacate, diphenyldihydrazide adipate, talc.
Further, in some embodiments of the invention, the lubricant is one or more of ethylene bis stearamide, erucamide, oleamide, glycerol tristearate.
Further, in some embodiments of the invention, the antioxidant is one or more of 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Further, in some embodiments of the invention, the hydrolysis inhibitor is one or both of a carbodiimide and a polycarbodiimide.
On the other hand, the invention also provides a preparation method of the heat-resistant high-strength dimensionally stable polylactic acid 3D printing material, which comprises the following steps:
(1) Adding the negative expansion filler, the dibasic ester and the catalyst into a mixer for mixing, then adding the hyperbranched polyester into the mixer for continuous mixing, and obtaining the hyperbranched polyester grafted modified negative expansion filler;
(2) Adding polylactic acid, a nucleating agent, a lubricant, an antioxidant and an anti-hydrolysis agent into the mixer in the step (1) and continuously mixing for 3min to obtain a premix;
(3) And (3) extruding and granulating the premix obtained in the step (2) to obtain the heat-resistant high-strength dimensionally stable polylactic acid 3D printing material.
Further, in some embodiments of the present invention, the mixing in step (1) is performed at a temperature of 120 to 150 ℃ and a stirring speed of 200 to 600rpm, preferably for 10 to 40 minutes.
Further, in some embodiments of the present invention, the step (1) is followed by adding the hyperbranched polyester and continuing the mixing at a temperature of 120 to 150℃and a stirring speed of 200 to 600rpm, preferably for 20 to 80 minutes.
Further, in some embodiments of the present invention, the extrusion pelletization in step (3) is melt extrusion pelletization carried out by adding a twin screw extruder at a temperature of 160 to 190℃and a screw speed of 200 to 600 rpm.
Advantages of the present invention over the prior art include, but are not limited to:
(1) Compared with the traditional low positive expansion coefficient filler, the invention can achieve the effect of remarkably reducing the crystallization shrinkage rate of the polylactic acid under the condition of lower filling quantity, thereby effectively reducing the filling quantity of the filler in the material, avoiding serious damage to the processing flow property of the polylactic acid caused by high-content filler, being beneficial to the extrusion of melt from a nozzle of a 3D printer, improving the bonding between extruded bars, and being capable of effectively improving the mechanical property of the product while remarkably improving the 3D printing processing property of the polylactic acid.
(2) According to the invention, the hyperbranched polyester is used for carrying out grafting modification on the negative thermal expansion filler, and the hyperbranched polyester grafted on the surface of the filler has a dendritic structure, so that the steric hindrance between filler particles can be effectively increased, and the dispersion of the filler in a polylactic acid matrix is obviously promoted, so that the larger defect formed by agglomeration of the filler in a product is avoided; the hyperbranched polyester grafted on the surface of the filler has better compatibility with the polylactic acid matrix, so that the interface strength between the polylactic acid matrix and the filler can be effectively improved; in addition, the hyperbranched polyester grafted on the surface of the filler is more flexible, so that the interface stress concentration caused by the crystallization shrinkage of the matrix and the cooling expansion of the filler can be effectively released, thereby avoiding the generation of large defects on the interface between the matrix and the filler, and the hyperbranched polyester grafted on the surface of the negative thermal expansion filler can obviously improve the mechanical property of the product.
(3) The hyperbranched polyester grafted on the surface of the filler has better compatibility with the polylactic acid matrix, and the larger free volume of the hyperbranched polyester can effectively reduce the entanglement degree between polylactic acid molecular chains, so that the flow property of a filling system is improved, the mutual fusion of 3D printing melt strips can be further promoted, the generation of larger defects in the product is avoided, and the mechanical property of the final product is improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is intended to be illustrative of the invention and not restrictive.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The singular forms include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or event may or may not occur, and that the description includes both cases where the event occurs and cases where the event does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
(1) 15 parts of zinc pyrophosphate, 0.5 part of dimethyl succinate and 0.05 part of tetrapropyl titanate are added into a high-speed mixer and mixed for 10min at a temperature of 150 ℃ and a stirring speed of 200 rpm; then adding 3 parts of hyperbranched polyester HyPerC100 into a high-speed mixer, and continuously mixing for 20min to obtain hyperbranched polyester grafted modified negative expansion filler;
(2) Adding 100 parts of polylactic acid with a melt index of 5g/10min and an optical purity of 95%, 3 parts of talcum powder, 0.1 part of ethylene bis stearamide, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol and 0.1 part of carbodiimide into a high-speed mixer in the step (1) and continuously mixing for 3min to obtain a premix;
(3) And (3) adding the premix obtained in the step (2) into a double-screw extruder to carry out melt extrusion granulation at the temperature of 160 ℃ and the screw rotation speed of 200rpm, thereby obtaining the polylactic acid modified material.
Example 2
(1) 20 parts of zinc pyrophosphate, 1 part of diethyl succinate and 0.1 part of tetrabutyl titanate are added into a high-speed mixer and mixed for 20min at the temperature of 120 ℃ and the stirring speed of 300 rpm; then adding 1 part of hyperbranched polyester HyPerC181 into a high-speed mixer, and continuously mixing for 40min to obtain hyperbranched polyester grafted modified negative expansion filler;
(2) Adding 100 parts of polylactic acid with the melt index of 10g/10min and the optical purity of 97%, 0.1 part of phenyl zinc phosphate, 0.2 part of erucamide, 0.2 part of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide and 0.3 part of polycarbodiimide into a high-speed mixer in the step (1) to continuously mix for 3min to obtain a premix;
(3) And (3) adding the premix obtained in the step (2) into a double-screw extruder to carry out melt extrusion granulation at the temperature of 170 ℃ and the screw rotating speed of 300rpm, thereby obtaining the polylactic acid modified material.
Example 3
(1) 25 parts of copper pyrophosphate, 1.5 parts of dimethyl adipate and 0.15 part of tetrabutyl titanate are added into a high-speed mixer and mixed for 30min at a temperature of 140 ℃ and a stirring speed of 500 rpm; then adding 8 parts of hyperbranched polyester HyPerC181 into a high-speed mixer, and continuously mixing for 60min to obtain hyperbranched polyester grafted modified negative expansion filler;
(2) Adding 100 parts of polylactic acid with a melt index of 15g/10min and an optical purity of 99%, 0.5 part of sebacic acid diphenyl dihydrazide, 0.3 part of oleamide, 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.8 part of polycarbodiimide into the high-speed mixer in the step (1) to continuously mix for 3min to obtain a premix;
(3) And (3) adding the premix obtained in the step (2) into a double-screw extruder to carry out melt extrusion granulation at the temperature of 180 ℃ and the screw rotating speed of 500rpm, thereby obtaining the polylactic acid modified material.
Example 4
(1) 30 parts of zinc pyrophosphate, 2 parts of diethyl adipate and 0.2 part of toluene sulfonic acid are added into a high-speed mixer and mixed for 40min at a temperature of 150 ℃ and a stirring speed of 600 rpm; then adding 5 parts of hyperbranched polyester HyPerC182 into a high-speed mixer, and continuously mixing for 80min to obtain hyperbranched polyester grafted modified negative expansion filler;
(2) Adding 100 parts of polylactic acid with a melt index of 20g/10min and an optical purity of 98%, 2 parts of adipic acid diphenyl dihydrazide, 0.5 part of glycerol tristearate, 0.5 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of polycarbodiimide into a high-speed mixer in the step (1) to continuously mix for 3min to obtain a premix;
(3) And (3) adding the premix obtained in the step (2) into a double-screw extruder to carry out melt extrusion granulation at the temperature of 190 ℃ and the screw rotating speed of 600rpm, thereby obtaining the polylactic acid modified material.
Comparative example 1
(1) 15 parts of calcium carbonate, 0.5 part of dimethyl succinate and 0.05 part of tetrapropyl titanate are added into a high-speed mixer and mixed for 10min at a temperature of 150 ℃ and a stirring speed of 200 rpm; then adding 3 parts of hyperbranched polyester HyPerC100 into a high-speed mixer, and continuously mixing for 20min to obtain hyperbranched polyester grafted and modified calcium carbonate;
(2) Adding 100 parts of polylactic acid with a melt index of 5g/10min and an optical purity of 95%, 3 parts of talcum powder, 0.1 part of ethylene bis stearamide, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol and 0.1 part of carbodiimide into a high-speed mixer in the step (1) and continuously mixing for 3min to obtain a premix;
(3) And (3) adding the premix obtained in the step (2) into a double-screw extruder to carry out melt extrusion granulation at the temperature of 160 ℃ and the screw rotation speed of 200rpm, thereby obtaining the polylactic acid modified material.
Comparative example 2
(1) 15 parts of zinc pyrophosphate, 0.5 part of dimethyl succinate and 0.05 part of tetrapropyl titanate are added into a high-speed mixer and mixed for 10min at the temperature of 150 ℃ and the stirring speed of 200rpm, so as to obtain modified negative expansion filler;
(2) Adding 100 parts of polylactic acid with a melt index of 5g/10min and an optical purity of 95%, 3 parts of talcum powder, 0.1 part of ethylene bis stearamide, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol and 0.1 part of carbodiimide into a high-speed mixer in the step (1) and continuously mixing for 3min to obtain a premix;
(3) And (3) adding the premix obtained in the step (2) into a double-screw extruder to carry out melt extrusion granulation at the temperature of 160 ℃ and the screw rotation speed of 200rpm, thereby obtaining the polylactic acid modified material.
Comparative example 3
(1) 15 parts of zinc pyrophosphate and 0.05 part of tetrapropyl titanate are added into a high-speed mixer and mixed for 10min at a temperature of 150 ℃ and a stirring speed of 200 rpm; then adding 3 parts of hyperbranched polyester HyPerC100 into a high-speed mixer, and continuously mixing for 20min to obtain hyperbranched polyester grafted modified negative expansion filler;
(2) Adding 100 parts of polylactic acid with a melt index of 5g/10min and an optical purity of 95%, 3 parts of talcum powder, 0.1 part of ethylene bis stearamide, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol and 0.1 part of carbodiimide into a high-speed mixer in the step (1) and continuously mixing for 3min to obtain a premix;
(3) And (3) adding the premix obtained in the step (2) into a double-screw extruder to carry out melt extrusion granulation at the temperature of 160 ℃ and the screw rotation speed of 200rpm, thereby obtaining the polylactic acid modified material.
Effect examples
To evaluate the properties of the modified materials obtained in examples 1 to 4 and comparative examples 1 to 3, the obtained modified materials were further extruded into 1.75mm strands at 190℃using a 3D printing strand extruder, and then the strands were subjected to a test by printing into mechanical test bars at a melting temperature of 200℃using a 3D printer.
The melt index of the material was measured at 190℃under a load of 2.16kg.
The tensile strength and elongation at break of the material were measured using 3D printed ASTM D638 standard tensile bars, with a tensile speed of 50mm/min.
The spline shrinkage of the material is calculated by taking the length L of a sample (uncrystallized) printed by unmodified PLA 4032D (Nature works) as a reference, and the calculation formula is as follows: spline shrinkage= (L) 4032D -L Examples/comparative examples )/L 4032D *100％。
The heat-resistant temperature of the material is obtained by testing ASTM D648 standard heat deformation spline obtained by 3D printing, the testing condition is the pressure of 0.45MPa, and the heating rate of 120 ℃/min.
The results of the above test are shown in Table 1.
Table 1 performance test data for each example and comparative example
| Test item | Fuse finger | Tensile Strength | Elongation at break | Sample strip shrinkage | Heat resistant temperature |
| Unit (B) | g/10min | MPa | ％ | ％ | ℃ |
| Example 1 | 4 | 60 | 7 | 0.78 | 125 |
| Example 2 | 5 | 66 | 5 | 0.56 | 127 |
| Example 3 | 14 | 68 | 6 | 0.43 | 128 |
| Example 4 | 11 | 67 | 7 | 0.37 | 130 |
| Comparative example 1 | 4 | 42 | 4 | 1.42 | 121 |
| Comparative example 2 | 1 | 28 | 2 | 1.25 | 113 |
| Comparative example 3 | 3 | 45 | 3 | 0.92 | 122 |
From the comparison of the data of example 1 and comparative example 1, it was found that zinc pyrophosphate, a negative thermal expansion filler, significantly reduced the shrinkage of the spline compared to calcium carbonate, a conventional filler, while also having a better improving effect on the heat resistance of the spline. From a comparison of the data of example 1 and comparative example 2, it was found that the addition of hyperbranched polyester in example 1 significantly improved the processability of the material, while it also effectively improved the degree of dispersion of the filler, thus ultimately significantly improving the tensile strength and heat resistance while also significantly reducing the shrinkage of the spline. In addition, it was found from the comparison of the data of example 1 and comparative example 3 that the dibasic ester as a coupling agent between the negative thermal expansion filler and the hyperbranched polyester plays an important role in improving the processability, tensile strength and the like of the material.
From the test data of examples 1 to 4 in Table 1, it was found that the shrinkage of the bars was significantly reduced by adding zinc pyrophosphate and copper pyrophosphate as both negative thermal expansion fillers to the material, and that the shrinkage of the bars was reduced to 0.5% or less when the negative thermal expansion filler content was 25% or more. Meanwhile, the added hyperbranched polyester obviously improves the interaction force between the filler and the matrix, so that the tensile strength and the heat-resistant temperature of the spline also rise along with the increase of the content of the negative thermal expansion filler, and the preferable formula is the formula of examples 3-4.
It will be readily appreciated by those skilled in the art that the foregoing is merely illustrative of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements or the like which fall within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The heat-resistant high-strength dimensionally stable polylactic acid 3D printing material is characterized by comprising the following components in percentage by weight: polylactic acid, negative expansion filler, hyperbranched polyester, dibasic ester, catalyst, nucleating agent, lubricant, antioxidant and anti-hydrolysis agent.
2. The heat-resistant high-strength dimensionally stable polylactic acid 3D printing material according to claim 1, wherein the heat-resistant high-strength dimensionally stable polylactic acid 3D printing material comprises the following components in parts by mass:
polylactic acid: 100 parts of
Negative expansion filler: 15-30 parts
Hyperbranched polyesters: 1 to 8 parts of
Dibasic ester: 0.5 to 2 parts
Catalyst: 0.05 to 0.2 part
Nucleating agent: 0.1 to 3 parts
And (3) a lubricant: 0.1 to 0.5 part
An antioxidant: 0.1 to 0.5 part
Hydrolysis inhibitor: 0.1 to 1 part;
preferably, the heat-resistant high-strength dimensionally stable polylactic acid 3D printing material comprises the following components in parts by mass:
polylactic acid: 100 parts of
Negative expansion filler: 25-30 parts
Hyperbranched polyesters: 5-8 parts
Dibasic ester: 1.5 to 2 parts
Catalyst: 0.15 to 0.2 part
Nucleating agent: 0.5 to 2 parts
And (3) a lubricant: 0.3 to 0.5 part
An antioxidant: 0.3 to 0.5 part
Hydrolysis inhibitor: 0.8 to 1 part.
3. The heat-resistant high-strength dimensionally stable polylactic acid 3D printing material according to claim 1, wherein the optical purity of the polylactic acid is not less than 95% and the melt index is 5-20 g/10min; preferably, the negative expansion filler is one or two of zinc pyrophosphate and copper pyrophosphate; preferably, the hyperbranched polyester is one or more of hyperbranched resins HyPerC100, hyPerC181, hyPerC 182.
4. The heat-resistant high-strength dimensionally stable polylactic acid 3D printing material according to claim 1, wherein the dibasic ester is one or more of dimethyl succinate, diethyl succinate, dimethyl adipate and diethyl adipate; preferably, the catalyst is one or more of tetrapropyl titanate, tetrabutyl titanate and methyl benzene sulfonic acid.
5. The heat-resistant high-strength dimensionally stable polylactic acid 3D printing material according to claim 1, wherein the nucleating agent is one or more of zinc phenylphosphate, diphenyl dihydrazide sebacate, diphenyl dihydrazide adipate and talcum powder; preferably, the lubricant is one or more of ethylene bis stearamide, erucamide, oleamide and glycerol tristearate.
6. The heat-resistant high-strength dimensionally stable polylactic acid 3D printing material according to claim 1, wherein the antioxidant is one or more of 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester; preferably, the hydrolysis inhibitor is one or both of carbodiimide and polycarbodiimide.
7. The method for preparing the polylactic acid 3D printing material with heat resistance, high strength and stable size according to any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) Adding the negative expansion filler, the dibasic ester and the catalyst into a mixer for mixing, then adding the hyperbranched polyester into the mixer for continuous mixing, and obtaining the hyperbranched polyester grafted modified negative expansion filler;
(2) Adding polylactic acid, a nucleating agent, a lubricant, an antioxidant and an anti-hydrolysis agent into the mixer in the step (1) and continuously mixing for 3min to obtain a premix;
(3) And (3) extruding and granulating the premix obtained in the step (2) to obtain the heat-resistant high-strength dimensionally stable polylactic acid 3D printing material.
8. The method for preparing a heat-resistant high-strength dimensionally stable polylactic acid 3D printing material according to claim 7, wherein the mixing in the step (1) is performed at a temperature of 120 to 150 ℃ and a stirring speed of 200 to 600rpm, preferably for 10 to 40 minutes.
9. The method for preparing the heat-resistant high-strength dimensionally stable polylactic acid 3D printing material according to claim 7, wherein the hyperbranched polyester is added in the step (1) and then mixed continuously at a temperature of 120-150 ℃ and a stirring speed of 200-600rpm, preferably for 20-80 min.
10. The method for preparing a heat-resistant high-strength dimensionally stable polylactic acid 3D printing material according to claim 7, wherein said extrusion granulation in said step (3) is melt extrusion granulation by adding a twin-screw extruder at a temperature of 160 to 190℃and a screw rotation speed of 200 to 600 rpm.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1856543A (en) * | 2003-09-22 | 2006-11-01 | 松下电器产业株式会社 | Flame-retardant resin composition, process for producing the same, and method of molding the same |
| JP2007091577A (en) * | 2005-09-05 | 2007-04-12 | Ohara Inc | Inorganic substance powder and composite material using the same |
| CN101857732A (en) * | 2009-04-10 | 2010-10-13 | 东丽纤维研究所（中国）有限公司 | Halogen-free flame-retardant thermoplastic resin composition |
| CN103804863A (en) * | 2013-09-02 | 2014-05-21 | 芜湖瀚博电子科技有限公司 | Biodegradable plastic line for three-dimensional (3D) printing |
| CN104725802A (en) * | 2015-03-27 | 2015-06-24 | 北京石油化工学院 | Preparation method of polylactic acid composite material for hot-melt 3D printing |
| WO2015165363A1 (en) * | 2014-04-30 | 2015-11-05 | 中国科学院化学研究所 | Material for 3d printing and preparation method therefor and product thereof |
| CN105482453A (en) * | 2016-02-03 | 2016-04-13 | 长春长光宇航复合材料有限公司 | Low thermal expansion coefficient cyanate ester resin composite and preparation method thereof |
| KR101812884B1 (en) * | 2016-07-05 | 2017-12-27 | 롯데케미칼 주식회사 | Polylactic acid composition of filament for improving printing speed |
| CN109867448A (en) * | 2017-12-04 | 2019-06-11 | 肖特股份有限公司 | Composite material, and the adhesive material including the composite material |
| CN110229001A (en) * | 2019-06-13 | 2019-09-13 | 北京科技大学 | A kind of preparation method for the negative thermal expansion material that can be used for sealing |
| CN111875940A (en) * | 2020-08-06 | 2020-11-03 | 苏州环诺新材料科技有限公司 | Toughened heat-resistant polylactic acid 3D printing wire and preparation method thereof |
| US20220135764A1 (en) * | 2019-07-23 | 2022-05-05 | Tokyo Institute Of Technology | Resin composition and resin molded body thereof |
-
2022
- 2022-10-27 CN CN202211326176.7A patent/CN116003980B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1856543A (en) * | 2003-09-22 | 2006-11-01 | 松下电器产业株式会社 | Flame-retardant resin composition, process for producing the same, and method of molding the same |
| JP2007091577A (en) * | 2005-09-05 | 2007-04-12 | Ohara Inc | Inorganic substance powder and composite material using the same |
| CN101857732A (en) * | 2009-04-10 | 2010-10-13 | 东丽纤维研究所（中国）有限公司 | Halogen-free flame-retardant thermoplastic resin composition |
| CN103804863A (en) * | 2013-09-02 | 2014-05-21 | 芜湖瀚博电子科技有限公司 | Biodegradable plastic line for three-dimensional (3D) printing |
| WO2015165363A1 (en) * | 2014-04-30 | 2015-11-05 | 中国科学院化学研究所 | Material for 3d printing and preparation method therefor and product thereof |
| CN104725802A (en) * | 2015-03-27 | 2015-06-24 | 北京石油化工学院 | Preparation method of polylactic acid composite material for hot-melt 3D printing |
| CN105482453A (en) * | 2016-02-03 | 2016-04-13 | 长春长光宇航复合材料有限公司 | Low thermal expansion coefficient cyanate ester resin composite and preparation method thereof |
| KR101812884B1 (en) * | 2016-07-05 | 2017-12-27 | 롯데케미칼 주식회사 | Polylactic acid composition of filament for improving printing speed |
| CN109867448A (en) * | 2017-12-04 | 2019-06-11 | 肖特股份有限公司 | Composite material, and the adhesive material including the composite material |
| CN110229001A (en) * | 2019-06-13 | 2019-09-13 | 北京科技大学 | A kind of preparation method for the negative thermal expansion material that can be used for sealing |
| US20220135764A1 (en) * | 2019-07-23 | 2022-05-05 | Tokyo Institute Of Technology | Resin composition and resin molded body thereof |
| CN111875940A (en) * | 2020-08-06 | 2020-11-03 | 苏州环诺新材料科技有限公司 | Toughened heat-resistant polylactic acid 3D printing wire and preparation method thereof |
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