CN105420837A - Completely-biodegradable high-roundness 3D printing filament and preparation method thereof - Google Patents
Completely-biodegradable high-roundness 3D printing filament and preparation method thereof Download PDFInfo
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- CN105420837A CN105420837A CN201510975816.0A CN201510975816A CN105420837A CN 105420837 A CN105420837 A CN 105420837A CN 201510975816 A CN201510975816 A CN 201510975816A CN 105420837 A CN105420837 A CN 105420837A
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- prints
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- wire material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention relates to a completely-biodegradable high-roundness 3D printing filament and a preparation method thereof. The 3D printing filament is composed of 60-89% of poly-L-lactic acid (PLLA), 5-20% of glass microspheres, 1-5% of poly-D-lactic acid (PDLA) and 5-15% of a PLA-PGA segmented copolymer. The 3D printing filament is prepared through extrusion at 170-190 DEG C in a drawing machine and then water-bath cooling and shaping at 40-60 DEG C. The 3D printing filament is good in roundness, high in strength, quick to crystallize, good in temperature resistance and good in toughness, and is suitable for 3D printing in various types.
Description
Technical field
The high circularity 3D that the present invention relates to a kind of complete biodegradable prints silk and preparation method thereof.
Background technology
3D prints the U.S. that thought originated from for 19 end of the centurys, and is developed in the eighties in 20th century and promote.It is a kind of rapid shaping technique, and it is a kind of based on mathematical model file, utilizes plastics, powdery metal etc. can jointing material, is carried out the technology of constructed object by the mode successively printed.
Realizing the mode that 3D prints has a variety of, and the technology of what at present development was the most ripe is exactly " fused deposition modeling " (FDM), whole flow process is molten plastic in shower nozzle, then just forms thin layer by the mode of depositing plastic material fiber.Conventional 3D prints resin material acrylonitrile-butadiene-styrene copolymer (ABS), nylon (PA), PLA (PLA) etc.
Biodegradable plastic, as the green substitute of common plastics, fundamentally can solve the problem of white pollution, and therefore, development complete biodegradable 3D printing technique is significant.And PLA is that current production capacity is maximum, the earliest, most widely used a kind of biodegradable plastic, so more about the research report of PLA 3D printing silk in exploitation.
CN103467950A and CN104693709A refer to a kind of lactic acid composite material printed for 3D respectively, they introduce polyvinyl alcohol and polyacrylate respectively in system, the nondegradable common plastics such as Merlon, in the 3D printed material that CN103804862A and CN103804862A mentions, high impact polystyrene (HIPS) is introduced respectively in PLA, methyl methacrylate-butadiene-styrene copolymer (MBS) and acrylic impact modifier, the non-degradable polymer such as thermoplastic elastomer (TPE), these methods are all used to the toughness improving PLA, but sacrifice the completely biodegradable of material, and do not consider at all different materials and PLA blended after, the circularity that different shrinkage factor causes 3D to print silk can be deteriorated, even do not consider that 3D prints the temperature tolerance of PLA product.
In sum, at present about PLA 3D print the report of silk mainly concentrate on PLA toughness reinforcing in, they ignore following problem: (1) different materials introduces impact 3D being printed to silk circularity; (2) 3D prints the crystallization rate of silk and the heatproof problem of printed product; (3) compatibility of flexibilizer and PLA and biodegradation sex chromosome mosaicism.
The present invention is just for these problems, introduce the high circularity that glass microsphere ensure that PLA wire drawing, PDLA powder is utilized to accelerate the crystallization rate of PLA, improve printed product temperature tolerance, add PLA-PGA block copolymer and improve its toughness, thus obtain that intensity is high, circularity good, crystallization is fast, temperature tolerance is good, the 3D of good toughness prints silk.
Summary of the invention
If adopt common drawing process, PLA and the blended 3D obtained of other materials are printed silk and easily occur following shortcoming:
(1) circularity of 3D printing silk is poor.We know, during any two kinds of plastic blends, due to molecular structure difference each other, cause shrinkage factor different, and therefore, the 3D that intermingling material is extruded prints silk circularity and will be deteriorated, and will cause the series of problems such as plug, fracture of wire in 3D print procedure like this.
(2) PLA 3D prints the product obtained after silk is printed by 3D printer, and crystallization rate is slow, and temperature tolerance is poor, and heat distortion temperature only has 50-55 DEG C, only has and could obtain high temperature tolerance by follow-up long-time crystallization treatment.This is because the crystallization of PLA needs certain temperature and time, that is, the method that we are difficult to be printed by direct 3D obtains high temperature tolerance PLA 3D printed product.
(3) PLA 3D prints silk and will have rigidity and toughness concurrently, and the introducing of flexibilizer can not cause 3D to print silk circularity variation because of poor compatibility, shrinkage factor difference.
The present invention is solved these problems targetedly by following technology.
(1) good rigidly of glass microsphere, circularity is good, and order number is high, is beneficial to dispersion.When glass microsphere and PLA blending extrusion, glass microsphere can not plastify, but be scattered in PLA matrix material uniformly with spherical shape, utilize the feature of the high rigidity of glass microsphere, high circularity, polymolecularity, wire drawing is played to the effect of " support " in drawing process, ensure that the PLA 3D extruded prints the circularity of silk.
(2) 300-500 object PDLA powder is utilized to be used as the crystallization nucleating agent of PLLA, this nucleator is different from the nucleator of other organic or inorganics, it and PLLA have good compatibility, cold afterwards≤190 DEG C of the compacted unders that mix of direct and PLLA resin are processed, without the need to twin-screw blending extrusion, also without the need to high temperature process, and different crystal formations and high-specific surface area can make it greatly accelerate the crystallization rate of PLLA, make to extrude the 3D obtained and print silk, crystallization rate very fast (crystallization time <1s), do not need through later crystallization process, just can obtain high-crystallinity and high temperature tolerance.If adopt PDLA resin and PLLA blended, PDLA content must more than 5%, and obtains high temperature tolerance through the high temperature 210-230 DEG C of blended PLA that just can make.
(3) toughness of silk is printed in order to improve PLA 3D, we are also as adopting the material such as thermoplastic elastomer (TPE), polyacrylate, poly butylene succinate (PBS), poly-hexane diacid-terephthalic acid-butylene terephthalate (PBAT) in other bibliographical informations, but select PLA-PGA block copolymer as the flexibilizer of PLA, not only compatibility is good, and complete biodegradable.
PDLA powder, we can by the flour mill of liquid nitrogen refrigerating, and through freezing, abrasive dust, sieving obtains 300-500 object PDLA powder.
The polylactic acid low polymer of PLA-PGA block copolymer by the molecular weight 1-4 ten thousand of mass ratio 1:1 and the polyglycolic acid of molecular weight 2-5 ten thousand, obtain after isocyanates chain extension.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.In embodiment, melting means unit is g/10min, test condition: 190 DEG C, 2.16kg.
The PLA-PGA block copolymer used in embodiment is by the PLA oligomer of mass ratio 1:1 (molecular weight 20,000) and PGA oligomer (molecular weight 30,000), under the chain extension of methyl diphenylene diisocyanate, reaction is obtained, molecular weight 9.5 ten thousand.
Embodiment 1
By 89%PLLA (fusing point 160 DEG C, melting means 15), 5% glass microsphere is (solid, 3000 orders), 1%PDLA powder (fusing point 170 DEG C, melting means 15,300 orders), after 5%PLA-PGA block copolymer (melting means 20) mixes, join in double screw extruder, at 160-180 DEG C, extruding pelletization obtains 3D and prints wire material, TENSILE STRENGTH 75MPa, notch impact strength 10KJ/m
2, heat distortion temperature 95 DEG C;
Above-mentioned steps being obtained material joins in wire drawing machine, at 170-190 DEG C, extrude wire drawing, and bath temperature is followed successively by 40 DEG C, filament diameter 1.5mm, circularity ± 0.002mm.
Embodiment 2
By 80%PLLA (fusing point 165 DEG C, melting means 12), 12% glass microsphere is (solid, 4000 orders), 3%PDLA powder (fusing point 170 DEG C, melting means 6.5,400 orders), after 8%PLA-PGA block copolymer (melting means 10) mixes, join in double screw extruder, at 160-180 DEG C, extruding pelletization obtains 3D and prints wire material, TENSILE STRENGTH 68MPa, notch impact strength 12KJ/m
2, heat distortion temperature 108 DEG C;
Above-mentioned steps being obtained material joins in wire drawing machine, at 170-190 DEG C, extrude wire drawing, and bath temperature is 50 DEG C, filament diameter 3.0mm, circularity ± 0.003mm.
Embodiment 3
By 60%PLLA (fusing point 170 DEG C, melting means 5.7), 20% glass microsphere is (hollow, 5000 orders), 5%PDLA powder (fusing point 160 DEG C, melting means 4.5,500 orders), after 15%PLA-PGA block copolymer (melting means 15) mixes, join in double screw extruder, at 160-180 DEG C, extruding pelletization obtains 3D and prints wire material, TENSILE STRENGTH 79MPa, notch impact strength 15KJ/m
2, heat distortion temperature 135 DEG C;
Above-mentioned steps being obtained material joins in wire drawing machine, at 170-190 DEG C, extrude wire drawing, and bath temperature is 60 DEG C, filament diameter 1.75mm, circularity ± 0.001mm.
Claims (8)
1. the high circularity 3D that the present invention relates to a kind of complete biodegradable prints silk, and this 3D prints that wire material gathers L-lactic acid (PDLA) powder by 60-89% PLLA (PLLA), 5-20% glass microsphere, 1-5%, 5-15%PLA-PGA block copolymer forms.
2. 3D according to claim 1 prints wire material, and it is characterized in that the D-lactic acid content of monomer of PLLA (PLLA) is 99.5-100%, fusing point is 160-170 DEG C, melting means≤15g/10min (190 DEG C, 2.16kg).
3. 3D according to claim 1 prints wire material, and it is characterized in that the order number of glass microsphere is 3000-5000 order, glass microsphere can be solid or hollow.
4. 3D according to claim 1 prints wire material, and it is characterized in that the L-lactic acid content of monomer of poly-L-lactic acid (PDLA) is 99.5-100%, fusing point is 160-170 DEG C, melting means≤15g/10min (190 DEG C, 2.16kg).
5. 3D according to claim 1 prints wire material, it is characterized in that the order number of poly-L-lactic acid (PDLA) powder is 300-500 order.
6. 3D according to claim 1 prints wire material, it is characterized in that the melting means≤20g/10min (190 DEG C, 2.16kg) of PLA-PGA block copolymer.
7. 3D according to claim 1 prints wire material, after it is characterized in that PLLA, glass microsphere, PDLA powder, PLA-PGA block copolymer mix, adds double screw extruder, and at 160-180 DEG C, extruding pelletization obtains 3D and prints wire material.
8. 3D according to claim 1 prints silk, and it is characterized in that its preparation method is extruded at 170-190 DEG C by wire drawing machine, the silk of pull-out obtains after 40-60 DEG C of water-bath cooling and shaping again.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510975816.0A CN105420837B (en) | 2015-12-22 | 2015-12-22 | A kind of high circularity 3D printing silk of complete biodegradable and preparation method thereof |
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| CN201510975816.0A CN105420837B (en) | 2015-12-22 | 2015-12-22 | A kind of high circularity 3D printing silk of complete biodegradable and preparation method thereof |
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| CN105420837A true CN105420837A (en) | 2016-03-23 |
| CN105420837B CN105420837B (en) | 2017-10-20 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106832827A (en) * | 2016-12-21 | 2017-06-13 | 成都新柯力化工科技有限公司 | A kind of heat endurance poly-lactic acid material for 3D printing and preparation method thereof |
| CN107199754A (en) * | 2017-06-14 | 2017-09-26 | 淄博成达塑化有限公司 | Biodegradable 3D printing silk of three layers of skin-core structure and preparation method thereof |
| CN107286609A (en) * | 2017-06-20 | 2017-10-24 | 广东波斯科技股份有限公司 | A kind of low-density thermal conductivity PLA 3D printing material and its preparation method and application |
| CN112920581A (en) * | 2021-04-01 | 2021-06-08 | 青岛科技大学 | Biodegradable nano composite material for 3D printing |
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| CN104231524A (en) * | 2014-07-23 | 2014-12-24 | 珠海天威飞马打印耗材有限公司 | Moulded wire and preparation method thereof |
| CN104530669A (en) * | 2014-12-18 | 2015-04-22 | 陈梓煜 | Modified polylactic material for 3D (three dimensional) printing and preparation method thereof |
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| CN103467950A (en) * | 2013-09-29 | 2013-12-25 | 成都新柯力化工科技有限公司 | 3D printing modified polylactic acid material and preparation method thereof |
| CN104231524A (en) * | 2014-07-23 | 2014-12-24 | 珠海天威飞马打印耗材有限公司 | Moulded wire and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832827A (en) * | 2016-12-21 | 2017-06-13 | 成都新柯力化工科技有限公司 | A kind of heat endurance poly-lactic acid material for 3D printing and preparation method thereof |
| CN107199754A (en) * | 2017-06-14 | 2017-09-26 | 淄博成达塑化有限公司 | Biodegradable 3D printing silk of three layers of skin-core structure and preparation method thereof |
| CN107199754B (en) * | 2017-06-14 | 2019-03-26 | 淄博成达塑化有限公司 | The biodegradable 3D printing silk and preparation method thereof of three layers of skin-core structure |
| CN107286609A (en) * | 2017-06-20 | 2017-10-24 | 广东波斯科技股份有限公司 | A kind of low-density thermal conductivity PLA 3D printing material and its preparation method and application |
| CN112920581A (en) * | 2021-04-01 | 2021-06-08 | 青岛科技大学 | Biodegradable nano composite material for 3D printing |
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Effective date of registration: 20170829 Address after: Hangzhou City, Zhejiang province 310004 City Road No. 588 Fei Jia Tang building 215 room 7 Applicant after: Hangzhou Seemore New Material Technology Co., Ltd. Address before: 315800, Zhejiang, Ningbo bonded area West Port West Avenue 1, 1 on the eastern side of the 1-2 floor Applicant before: NINGBO KEYINGSHI ENVIRONMENTAL PROTECTION MATERIAL CO., LTD. |
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