AU2019100615A4 - Polylactic acid 3D printing material and preparation method thereof - Google Patents
Polylactic acid 3D printing material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polylactic acid 3D printing material and a preparation method thereof, and belongs to the technical field of polymer materials. The polylactic acid 3D printing material of the present invention comprises the following raw materials in parts by weight: (a) 40 to 95 parts of crystalline or semi-crystalline polylactic acid, (b) 5 to 60 parts of amorphous polylactic acid, and (c) The processing aid is 0 to 1.0 part; in the polylactic acid 3D printing material, the weight of the right-handed polylactic acid accounts for 0.5% to 8% of the total weight of the polylactic acid. The invention adopts two kinds of polylactic acid with different optical purity as raw materials, reasonably distributes the proportional relationship between the two, and defines the content of the right-handed polylactic acid, thereby obtaining a polylactic acid 3D printing material with good aging resistance. Studies have shown that the polylactic acid 3D printing material of the present invention has a viscosity retention rate of 70% or more after being placed in a constant temperature and humidity chamber (temperature 60 ° C, humidity 60%) for 12 days.
Description
Polylactic acid 3D printing material and preparation method thereof
Technical field
The invention relates to a polylactic acid 3D printing material and a preparation method thereof, and belongs to the technical field of polymer materials.
Background technique
The starch-containing corn is produced by modern biotechnology to produce a colorless and transparent liquid, lactic acid, which is then subjected to a special polymerization process to produce a granular polymer material, polylactic acid (PLA). PLA has the best tensile strength and ductility and can be produced by various common processing methods such as melt extrusion, injection molding, blown film forming, foam molding and vacuum forming. However, at this stage, PLA is used as a general-purpose plastic, especially 3D printing consumables. The large-area promotion and application is still limited. This is mainly due to the serious brittleness of polylactic acid, and the notched impact strength is less than 3KJ/m2, which severely limits its widely used. Therefore, how to improve the toughness of polylactic acid without affecting its extrusion stability is a problem that must be solved in expanding the application of polylactic acid in 3D printing consumables.
The patent entitled A 3D Printing PLA Consumable and a Method for Preparing the Same (Application No.: 201510069937.9) provides a 3D printing PLA consumable and a preparation method thereof, which are made of the following materials by weight: PLA 99.3-99.7%, pigment 0.1-0.3%, and adjuvant 0.2-0.4%, but not mentioned for polylactic acid D content and wire aging properties.
Summary of the invention
An object of the present invention is to provide a polylactic acid 3D printing material having good aging resistance and a method for preparing the same, which overcomes the deficiencies of the prior art.
In order to achieve the above object, the technical solution adopted by the present invention is: a polylactic acid 3D printing material comprising the following raw materials in parts by weight:
(a) 40 to 95 parts of crystalline or semi-crystalline polylactic acid, (b) 5 to 60 parts of amorphous polylactic acid, and (c) 0 to 1.0 parts of processing aids;
In the polylactic acid 3D printing material, the weight of the right-handed polylactic acid accounts for 0.5% to 8% of the total weight of the polylactic acid.
Polylactic acid includes D-polylactic acid and L-polylactic acid. The optical rotation of pure L-polylactic acid is -156°, and the optical rotation of pure D-polylactic acid is 156°. Optical purity directly affects the crystallinity and crystallinity of polylactic acid. The higher the optical purity, the faster the crystallization rate of polylactic acid and the higher the crystallinity. As the optical purity decreases, the extinction value of the polylactic acid rotation decreases. Pure poly-d-polylactic acid or L-polylactic acid can reach a melting point of 180 ° C, has a high degree of crystallinity, and has a very low degradation rate. As the optical purity of PLA decreases, the melting point and crystallinity of PLA decrease until it becomes amorphous. The degradability of PLA is enhanced, and its mechanical properties and rheological properties are also changed
2019100615 06 Jun 2019 accordingly. Therefore, the properties of polylactic acid materials are closely related to their optical purity.
The above crystalline or semicrystalline polylactic acid is used as a continuous phase, and amorphous polylactic acid is used as a dispersed phase. The invention adopts two kinds of polylactic acid with different optical purity as raw materials, reasonably distributes the proportional relationship between the two, and defines the content of the right-handed polylactic acid, thereby obtaining a polylactic acid 3D printing material with good aging resistance. Studies have shown that the polylactic acid 3D printing material of the present invention has a viscosity retention rate of 70% or more after being placed in a constant temperature and humidity chamber (temperature 60 ° C, humidity 60%) for 12 days.
In the above technical solution, the total weight of the polylactic acid is the sum of (a) the weight of the crystalline or semi-crystalline polylactic acid and (b) the amorphous polylactic acid. The test method of D-polylactic acid (poly-lactic acid in the right-handed body) is: using the Agilent HP6890 gas chromatograph, the complex formed by the molecules of the cyclodextrin in the gas chromatography column has different equilibrium constants, and the two pairs of lactic acid The complexing ability of the body is different, so that it is easy to separate the gas chromatograph, and the percentage of the two enantiomers in the polylactic acid is obtained by this method. The specific steps are as follows: 1. Prepare a standard solution with a known content of dextran polylactic acid, and record the peak time of the standard solution in the chromatogram; 2. Obtain the standard curve equation according to the concentration and peak area of the standard sample; The chromatogram of the sample under the same chromatographic conditions was compared with the polylactic acid standard solution. The L-polylactic acid and D-polylactic acid in the sample were determined according to the retention time. The content of D-lactic acid in the sample was calculated by external standard method. That is, the content of the right-handed body of polylactic acid.
As a preferred embodiment of the polylactic acid 3D printing material of the present invention, the polylactic acid 3D printing material comprises the following parts by weight of a preparation material:
(a) 50 to 90 parts of crystalline or semi-crystalline polylactic acid, (b) 10 to 50 parts of amorphous polylactic acid, and (c) 0 to 1.0 parts of processing aid.
The weight ratio of the crystalline or semi-crystalline polylactic acid to the non-crystalline polylactic acid of the present invention affects the aging resistance of the obtained polylactic acid 3D printing material. Studies have shown that the resulting polylactic acid 3D printing material has better aging resistance properties within the preferred parts by weight.
As a preferred embodiment of the polylactic acid 3D printing material of the present invention, in the polylactic acid 3D printing material, the weight of the right-handed polylactic acid accounts for 1.4% to 6% of the total weight of the polylactic acid.
As a preferred embodiment of the polylactic acid 3D printing material of the present invention, the amorphous polylactic acid has an average particle diameter of less than 1 pm.
As a preferred embodiment of the polylactic acid 3D printing material of the present invention, the processing aid is a lubricant.
As a more preferred embodiment of the polylactic acid 3D printing material of the present invention, the processing aid is a hard ester amide, an oleic acid amide, an erucamide, a zinc
2019100615 06 Jun 2019 stearate, a polymer complex of a metal soap, and an ethylene double At least one of stearamide, polyethylene wax, and silicone lubricant. The processing aid may be selected from one, two or more of the substances, but the processing aid is not limited to the substance.
The invention also provides a preparation method of the above polylactic acid 3D printing material, which comprises the following steps:
(1) weighing each substance in the raw material of the polylactic acid 3D printing material by weight, and mixing uniformly to obtain a mixture;
(2) The mixture obtained in the step (1) is put into a twin-screw extruder, extruded, and granulated to obtain a composition;
(3) The composition obtained in the step (2) was drawn on a single-screw extruder to obtain the polylactic acid 3D printing material.
The polylactic acid 3D printing material obtained by the above method is a 3D printed wire.
As a preferred embodiment of the preparation method of the polylactic acid 3D printing material of the present invention, in the step (2), the temperature of the twin-screw extruder is 160 to 180 °C.
As a preferred embodiment of the preparation method of the polylactic acid 3D printing material of the present invention, in the step (3), the conditions for drawing the wire on the single-screw extruder are as follows: the speed of the wire drawing extrusion is 10 - 60 Kg / h, The wire diameter of the extruded wire is 1.5-3.5 cm, and the temperature of the water tank is 40-60 °C.
Compared with the prior art, the beneficial effects of the present invention are as follows: the invention selects two kinds of polylactic acid with different optical purity as raw materials, reasonably distributes the proportional relationship between the two, and defines the content of the right-handed polylactic acid, thereby obtaining a good ratio. A lactic acid 3D printed material with aging resistance. Studies have shown that the polylactic acid 3D printing material of the present invention has a viscosity retention rate of 70% or more after being placed in a constant temperature and humidity chamber (temperature 60 ° C, humidity 60%) for 12 days.
Detailed ways
The present invention will be further described with reference to specific embodiments in order to better illustrate the objects, aspects and advantages of the invention.
In the following examples, the material viscosity is tested at 25 ° C, accurately weigh 0.1250 + 0.0005 g sample dissolved in 25 ml (o-dichlorobenzene: phenol = 2:3 mass ratio) solution, heated at 110 ° C Stir until the resin is completely dissolved and measured by a viscometer. The viscosity value is retained in two digits after the decimal point.
Viscosity retention rate: viscosity after aging / initial viscosity * 100%.
Example 1
An embodiment of the polylactic acid 3D printing material of the present invention, the preparation materials of the polylactic acid 3D printing material of the present embodiment are as described in Table 1.
The preparation method of the polylactic acid 3D printing material according to this embodiment is as follows:
(1) weighing each substance in the raw material of the polylactic acid 3D printing material by weight, and mixing uniformly to obtain a mixture;
2019100615 06 Jun 2019 (2) The mixture obtained in the step (1) is put into a twin-screw extruder, extruded at 160-180 ° C, and granulated to obtain a composition;
(3) The composition obtained in the step (2) is drawn on a single-screw extruder to obtain the polylactic acid 3D printing material; wherein the conditions for drawing the wire on the single-screw extruder are as follows: the speed of the wire drawing extrusion is 10 -60 Kg/h, the wire diameter of the extruded wire is 1.5-3.5 cm, and the temperature of the water tank is 40-60 ° C: the first stage sink is 40 ’ C, and the second section sink is 50 ’ C.
Example 2~7
The preparation materials of the polylactic acid 3D printing materials described in Examples 2 to 7 are as described in Table 1; the preparation methods of the polylactic acid 3D printing materials described in Examples 2 to 7 are the same as those in Example 1.
The polylactic acid 3D printing materials obtained in Examples 1 to 7 were allowed to stand under constant temperature and humidity (temperature: 60 ° C, humidity: 60%) for 12 days, and the viscosity retention ratio thereof was measured. The results are shown in Table 1.
| ~—^^Exa m p 1 e Raw material | Examplel | Example2 | Example3 | Example4 | Example5 | Example6 | Example7 | |
| Crystalline or semi-crystalline polylactic acid | Parts by weight | 90 | 90 | 80 | 50 | 90 | 95 | 40 |
| Amorphous polylactic acid | Parts by weight | 10 | 10 | 20 | 50 | 10 | 5 | 60 |
| Average particle size /pm | 0.5 | 0.3 | 0.7 | 0.8 | 0.95 | 0.5 | 0.3 | |
| In polylactic acid 3D printing materials, the weight of D-polylactic acid as a percentage of the total weight of polylactic acid /% | 2.0 | 2.5 | 3.0 | 6 | 1.4 | 0.5 | 8 | |
| Processing aids | Substance | Ethylene bis stearamide | Ethylene bis stearamide | Ethylene bis stearamide | Ethylene bis stearamide | Zinc stearate | Polyethylene wax | Oleic acid amide |
| Parts by weight | 0 | 0.2 | 0.2 | 0.2 | 0.2 | 0.6 | 1.0 | |
| Viscosity retention rate /% | 75 | 80 | 78 | 76 | 82 | 74 | 74 |
It can be seen from Table 1 that according to the present invention, two kinds of polylactic acid having different optical purity are selected as raw materials, the proportional relationship between the two is reasonably distributed, and the content of the right-handed polylactic acid is limited, and the polylactic acid 3D printing material with good aging resistance can be obtained. . The polylactic acid 3D printing material of the present invention has a viscosity retention rate of 70% or more after being placed in a constant temperature and humidity chamber (temperature: 60 ° C, humidity: 60%) for 12 days.
Effect example 1
2019100615 06 Jun 2019
The average particle diameter of the amorphous polylactic acid of the present invention affects the aging resistance of the obtained polylactic acid 3D printing material. According to the method of Example 1, the test group and the control group polylactic acid 3D printing material are prepared and prepared. The obtained polylactic acid 3D printing material was allowed to stand under constant temperature and humidity (temperature: 60 ° C, humidity: 60%) for 12 days, and the viscosity retention ratio thereof was measured. The results are shown in Table 2.
Among them, the experimental group and the control group have different polylactic acid 3D printing materials only in that the average particle diameter of the amorphous polylactic acid is different. Specifically, the polylactic acid 3D printing materials of the test group and the control group are made of the following raw materials by weight. Form: (a) 40 to 95 parts of crystalline or semi-crystalline polylactic acid, (b) 5 to 60 parts of amorphous polylactic acid, and (c) 0 to 1.0 part of processing aid; the polylactic acid 3D printing material The weight of the right-handed polylactic acid accounts for 0.5% to 8% of the total weight of the polylactic acid; the processing aid is a lubricant.
Table 2
| Test group 1 | Test group 2 | Test group 3 | Control group 1 | Control group 2 | Control group 3 | Control group 4 | |
| Average particle size of amorphous polylactic acid /pm | 0.8 | 0.9 | 0.95 | 1.0 | 1.1 | 1.2 | 1.5 |
| Viscosity retention rate /% | 76 | 81 | 82 | 68 | 67 | 65 | 55 |
As can be seen from Table 2, when the average particle diameter of the amorphous polylactic acid is less than 1 pm, the obtained polylactic acid 3D printing material has better aging resistance.
Effect example 2
This effect example examines the effect of the temperature of the water tank on the aging resistance of the obtained polylactic acid 3D printing material when preparing the polylactic acid 3D printing material.
In this effect example, a test group polylactic acid 3D printing material was prepared according to the method of Example 1. Specifically, the test group polylactic acid 3D printing material was prepared from the following parts by weight: (a) crystalline or semi-crystalline poly 40 to 95 parts of lactic acid, (b) 5 to 60 parts of amorphous polylactic acid, and (c) 0 to 1.0 parts of processing aid; in the polylactic acid 3D printing material, the weight of the right-handed polylactic acid accounts for polylactic acid The total weight of the amorphous polylactic acid is less than 1 pm;
2019100615 06 Jun 2019 the processing aid is a lubricant.
In this effect example, a polylactic acid 3D printing material of the control group was prepared at the same time. The difference between the polylactic acid 3D printing material of the control group and the polylactic acid 3D printing material of the experimental group was only that the temperature of the water tank was 65-75 ° C during preparation.
The viscosity retention of the polylactic acid 3D printing material in the test group and the control group was examined, and the results are shown in Table 3.
Table 3
| Test group | Control group | |
| Viscosity retention rate /% | 78 | 60 |
It can be seen from Table 3 that the polylactic acid 3D printing material obtained by the method of the present invention has better aging resistance.
Effect example 3
The weight ratio of the crystalline or semi-crystalline polylactic acid to the non-crystalline polylactic acid of the present invention affects the aging resistance of the obtained polylactic acid 3D printing material, and the effect example changes the crystalline or semi-crystalline polylactic acid and the amorphous type. The polylactic acid 3D printing materials were prepared according to the method described in Example 1 in the weight ratio of polylactic acid, and the aging resistance of the polylactic acid 3D printing materials of each test group and the control group was tested. In this effect example, the test group and the control group polylactic acid 3D printing material are prepared from the following preparation materials: (a) crystalline or semi-crystalline polylactic acid, (b) amorphous polylactic acid, and (c) processing aid In the polylactic acid 3D printing material, the weight of the right-handed polylactic acid accounts for 0.5% to 8% of the total weight of the polylactic acid; the average particle diameter of the amorphous polylactic acid is less than 1 pm; the processing aid is lubricated The processing aid is 0-1.0 parts by weight, and the weight of the crystallized or semi-crystalline polylactic acid and the non-crystalline polylactic acid in the polylactic acid 3D printing material of each test group and the control group are different, and the weight of the two The parts and aging resistance are shown in Table 4.
Table 4
| Test group 1 | Test group 2 | Test group 3 | Test group 4 | Test group 5 | Control group 1 | Control group 2 | Control group 3 | Control group 4 | |
| Crystalline or semi-crystalline polylactic acid/parts of weight | 90 | 50 | 80 | 95 | 40 | 35 | 30 | 97 | 98 |
2019100615 06 Jun 2019
| Amorphous polylactic acid / parts of weight | 10 | 50 | 20 | 5 | 60 | 65 | 70 | 3 | 2 |
| Viscosity retention rate /% | 78 | 77 | 78 | 74 | 74 | 65 | 56 | 63 | 60 |
It can be seen from Table 4 that when the weight ratio of the crystalline or semi-crystalline polylactic acid to the non-crystalline polylactic acid is within the range of the present invention, the aging resistance of the polylactic acid 3D printing material is significantly better than the weight ratio of the two. In the case of the present invention, especially when the weight ratio of the two is (50 to 90): (10 to 50), the aging resistance of the polylactic acid 3D printing material is better.
Effect example 4
This effect example investigates the effect of the weight percentage of D-polylactic acid on the polylactic acid 3D printing material on the aging resistance of the obtained polylactic acid 3D printing material when preparing the polylactic acid 3D printing material.
This effect example changed the weight percentage of D-polylactic acid in the polylactic acid 3D printing material, and different experimental group and control group polylactic acid 3D printing materials were prepared according to the method described in Example 1, and the test groups and the control group were tested. Aging resistance of lactic acid 3D printing materials. In this effect example, the test group and the control group polylactic acid 3D printing material are prepared from the following raw materials by weight: (a) 40-95 parts of crystalline or semi-crystalline polylactic acid, (b) amorphous polylactic acid 5 to 60 parts, and (c) 0 to 1.0 parts of the processing aid; the amorphous polylactic acid has an average particle diameter of less than 1 pm; and the processing aid is a lubricant. The polylactic acid 3D printing materials of each test group and the control group only differed in the weight percentage of the right-handed polylactic acid, and the weight percentage of the right-handed polylactic acid and the aging resistance were as shown in Table 5.
Table 5
| Test group 1 | Test group 2 | Test group 3 | Test group 4 | Test group 5 | Control group 1 | Control group 2 | Control group 3 | Control group 4 | |
| In polylactic acid 3D printing materials, | 1.4 | 6 | 4.0 | 0.5 | 8 | 0.3 | 0.2 | 8.5 | 9 |
2019100615 06 Jun 2019
| the weight of D-polylactic acid as a percentage of the total weight of polylactic acid | |||||||||
| Viscosity retention rate /% | 81 | 77 | 78 | 75 | 74 | 68 | 65 | 60 | 50 |
It can be seen from Table 5 that when the weight percentage of the right-handed polylactic acid in the polylactic acid 3D printing material is within the range of the present invention, the aging resistance of the polylactic acid 3D printing material is significantly better than the weight percentage thereof, which is not within the scope of the present invention. In the case, especially when the weight percentage thereof is 1.4% to 6%, the aging resistance of the polylactic acid 3D printing material is better.
It should be noted that the above embodiments are only intended to illustrate the technical solutions of the present invention and are not intended to limit the scope of the present invention, although the present invention will be described in detail with reference to the preferred embodiments, The technical solutions of the present invention may be modified or equivalently substituted without departing from the spirit and scope of the technical solutions of the present invention.
Claims (3)
- There is one page of the claims only.2019100615 06 Jun 20191. A polylactic acid 3D printing material comprising the following raw materials in parts by weight:(a) 40 to 95 parts of crystalline or semi-crystalline polylactic acid, (b) 5 to 60 parts of amorphous polylactic acid, and (c) 0 to 1.0 parts of processing aids;In the polylactic acid 3D printing material, the weight of the right-handed polylactic acid accounts for 0.5% to 8% of the total weight of the polylactic acid.2. The polylactic acid 3D printing material according to claim 1, comprising the following parts by weight of a preparation material:(a) 50 to 90 parts of crystalline or semi-crystalline polylactic acid, (b) 10 to 50 parts of amorphous polylactic acid, and (c) 0 to 1.0 parts of processing aid.3. The polylactic acid 3D printing material according to claim 1 or 2, wherein in the polylactic acid 3D printing material, the weight of the right-handed polylactic acid accounts for 1.4% to 6% of the total weight of the polylactic acid.4. The polylactic acid 3D printing material according to claim 1, wherein the amorphous polylactic acid has an average particle diameter of less than 1 pm.5. The polylactic acid 3D printing material according to claim 1, wherein the processing aid is a lubricant.6. The polylactic acid 3D printing material according to claim 1, wherein the processing aid is a polymer ester of a hard ester amide, an oleic acid amide, an erucamide, a zinc stearate or a metal soap, At least one of ethylene bis stearamide, polyethylene wax, and silicone lubricant.7. The method for preparing a polylactic acid 3D printing material according to any one of claims 1 to 6, comprising the steps of:(1) weighing each substance in the raw material of the polylactic acid 3D printing material by weight, and mixing uniformly to obtain a mixture;
- (2) The mixture obtained in the step (1) is put into a twin-screw extruder, extruded, and granulated to obtain a composition;
- (3) The composition obtained in the step (2) was drawn on a single-screw extruder to obtain the polylactic acid 3D printing material.8. The method for preparing a polylactic acid 3D printing material according to claim 7, wherein in the step (2), the temperature of the twin-screw extruder is 160-180 °C.9. The method for preparing a polylactic acid 3D printing material according to claim 7, wherein in the step (3), the conditions for drawing the wire on the single-screw extruder are as follows: the speed of the wire drawing extrusion is 10 - 60 Kg / h, the wire diameter of the extruded wire is 1.5-3.5 cm, and the temperature of the water tank is 40-60 ° C.
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| AUPCT/CN2019/088826 | 2019-05-28 | ||
| PCT/CN2019/088826 WO2019237914A1 (en) | 2018-06-15 | 2019-05-28 | Polylactic acid 3d printing material and preparation method therefor |
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| AU2019100615A4 true AU2019100615A4 (en) | 2019-07-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150503A (en) * | 2021-06-08 | 2021-07-23 | 明丹医疗科技有限公司 | 3D printing composite material suitable for medical treatment and aviation and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150503A (en) * | 2021-06-08 | 2021-07-23 | 明丹医疗科技有限公司 | 3D printing composite material suitable for medical treatment and aviation and preparation method thereof |
| CN113150503B (en) * | 2021-06-08 | 2022-07-01 | 明丹医疗科技有限公司 | 3D printing composite material suitable for medical treatment and aviation and preparation method thereof |
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