CN103665802A - Preparation method of polylactic acid material for 3D (three-dimensional) printing - Google Patents
Preparation method of polylactic acid material for 3D (three-dimensional) printing Download PDFInfo
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- CN103665802A CN103665802A CN201310620288.8A CN201310620288A CN103665802A CN 103665802 A CN103665802 A CN 103665802A CN 201310620288 A CN201310620288 A CN 201310620288A CN 103665802 A CN103665802 A CN 103665802A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
Abstract
The invention discloses a preparation method of a polylactic acid material for 3D (three-dimensional) printing. The polylactic acid material is toughened and modified by an inorganic nano material. The method comprises the steps as follows: firstly, surface organic modification is performed on a coupling agent for a nano inorganic toughening agent with an ultrasonic treatment technology, then the modified nano inorganic toughening agent, polylactic acid, a plasticizer and a dispersing agent are ground, dispersed and mixed, and finally, the toughened and modified polylactic acid material applicable to a 3D printing technology is prepared through an extruding granulation and drawing technology. According to the method, defects that existing polylactic acid materials for the 3D printing are poor in toughness and processability are overcome, and the method is simple to operate and capable of facilitating industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of 3D printed material, be specifically related to a kind of preparation method of the poly-lactic acid material of printing for 3D.
Background technology
3D printing technique claims again to increase material manufacturing technology, be actually a kind of emerging technology in rapid shaping field, it is a kind ofly to take digital model file as basis, uses powdery metal or the plastics etc. can jointing material, carrys out the technology of constructed object by the mode of successively printing.Ultimate principle is lamination manufacture, successively increases the technology that material generates 3D solid.At present, 3D printing technique is divided into again individual 3D printing technique and industrial 3D printing technique, and individual 3D printing technique has been subject to each side personage's high praise and has liked, prospect is very wide.
In individual 3D printing technique, conventional a kind of technical matters is that melt extruded is piled up forming technique (FDM), principle is to utilize thermoplastic, polymeric materials under molten state, from shower nozzle, squeeze out, solidify the thin layer that forms outline shape, then stack finally forms product from level to level.The macromolecular material that therefore individual 3D prints need to have good processing characteristics, not only to there is lower melt temperature, good melt fluidity and fast cooling time, also must there is very little cooling shrinking percentage and the structure of homogeneous, so just can when 3D printing shaping, not occur that interiors of products stress distribution is uneven different with cooling shrinking percentage, causes the underproof problem of the product printing.
Conventional individual 3D printing macromolecular material is mainly poly(lactic acid), ABS resin (acrylonitrile-butadiene-styrene terpolymer), nylon etc. in the market, and because poly(lactic acid) has nontoxic, without pungent smell, higher tensile strength, modulus of compression, melt temperature is lower, good biocompatibility, biodegradability, cooling shrinking percentage is little, and the plurality of advantages such as transparent easy dyeing are more subject to liking of people and pay close attention to; But the matter that poly(lactic acid) has is hard, toughness is poor, lack flexibility and elasticity, very easily diastrophic drawbacks limit its application on individual 3D printing technique.
At present for poly(lactic acid) as the modification technology documents and materials of individual 3D printed material also seldom.Due to the backwardness of technological method and equipment, the traditional material modified and method of many uses is carried out the poly-lactic acid material of modification and is not suitable for individual 3D printing technique.In traditional method of modifying, the material modified of filling blend do not spread out completely in poly(lactic acid) system, thereby cause when 3D printing shaping interiors of products stress distribution uneven different with cooling shrinking percentage, processing characteristics obviously reduces, thereby can the poly-lactic acid material after selecting correct modification method for preparing to modification meet and be suitable for 3D printing technique is very crucial to the requirement of material.
China Patent Publication No. CN103146164A discloses a kind of for nano material toughened poly-lactic acid material of rapid shaping and preparation method thereof, the method is to utilize twin screw extruder to carry out blending extrusion modification to polyacrylic acid ester microsphere and poly(lactic acid), improved the defect of poly(lactic acid) poor toughness, but polyacrylic acid ester microsphere add the heterogeneity that has caused poly(lactic acid) system structure, processing characteristics obviously reduces, and has had a strong impact on the printing shaping of product.
China Patent Publication No. CN103087489A discloses a kind of modified polylactic acid material and preparation method thereof, the method uses polyether polyamide elastomer and polynite as properties-correcting agent, with twin screw extruder, do modified device, tensile strength and the toughness of poly(lactic acid) have been strengthened, but in the method directly by polyether polyamide elastomer, twin screw blend instrument blending extrusion for polynite and poly(lactic acid), equipment is single, the blend time is short, cause the polyether polyamide elastomer of filling blend and polynite not to spread out completely in poly(lactic acid) system and form the structure of homogeneous, during printing shaping, interiors of products stress dispersion is uneven different with cooling shrinking percentage, poor processability, thereby toughening modified polylactic acid material prepared by this preparation method is not suitable for 3D printing technique.
China Patent Publication No. CN102134381A discloses a kind of modified polylactic acid material and preparation method thereof, in the method, toughness reinforcing heat-resistant elastomer properties-correcting agent and polylactic acid blend are extruded to modification, improved the defect of the poor toughness of poly(lactic acid), also improved the heat resisting temperature of poly(lactic acid), but in the method, be also the method for modifying that adopts direct blending extrusion, reduce the processing characteristics of poly(lactic acid), be not also suitable for 3D printing technique.
Above-mentioned is all to adopt co-blending elastic body to improve toughness, and owing to having adopted elastomerics, preparation method is single backwardness also, and the poly(lactic acid) processing characteristics after modification obviously reduces, and is not suitable for 3D and prints.Poly-lactic acid material is wanted in individual 3D printing technique, to be widely used, the material modified selection of polydactyl acid and preparation method are very important, and can be affects modified polylactic acid material meet and be suitable for the important factor of 3D printing technique to the requirement of material.
Summary of the invention
For current poly-lactic acid material modification method for preparing, exist equipment single, the defect that technological method falls behind, the present invention proposes a kind of preparation method of the poly-lactic acid material of printing for 3D.For achieving the above object, the present invention first utilizes ultrasonication technology that nano inorganic toughner is carried out to organic modification of surface with coupling agent, again the nano inorganic toughner through modification is ground, disperses, mixed with poly(lactic acid), softening agent, dispersion agent, finally by crossing extruding pelletization, drawing process, make the toughening modified polylactic acid material that is applicable to 3D printing.
The concrete preparation method of a kind of poly(lactic acid) of printing for 3D of the present invention is as follows:
1) coupling agent of the nano inorganic toughner of 10-25 weight part, 0.5-2 weight part, appropriate solvent are added to people in reactor, under the stirring velocity of the temperature of 60 ℃, 100-300r/min, with ultrasonication reaction 1-3h discharging, dry, grind and obtain the nano inorganic toughner that organic modification of surface is processed;
2) nano inorganic toughner and the poly(lactic acid) of 60-85 weight part the organic modification of surface that obtains in step 1) processed be, the dispersion agent of the softening agent of 1-3 weight part, 1-5 weight part joins in planetary ball mill, grinds, dispersion, combination treatment 1-2h discharging obtain mixture under the speed of 300-450r/min;
3) by step 2) the twin screw extruder mixing extruding pelletization for mixture that obtains, the time that material stops in forcing machine is 5-8 minute.Double-screw extruder screw diameter is 75mm, and length-to-diameter ratio is 52:1, and extruder temperature is set as successively: 120-125 ℃, 125-135 ℃, 135-145 ℃, 130-140 ℃, 135-140 ℃, die head temperature 145-155 ℃;
4) by step 3) in institute granulation with single screw extrusion machine, extrude and be processed into the filament that diameter is 1.75mm, 3mm after being dried 2-3 hour with drying baker at the temperature of 50 ℃, diameter error is in 5%.Single screw extrusion machine screw diameter is 75mm, and length-to-diameter ratio is 20:1, and extruder temperature is set as successively: 125-135 ℃, 130-140 ℃, 135-145 ℃, 140-150 ℃, 145-155 ℃, die head temperature 145-155 ℃.
Preparation method in a kind of poly(lactic acid) of printing for 3D, wherein said planetary ball mill is to utilize the rolling at a high speed in grinding pot of abrasive material and test portion, material is produced strong shear, impacts, rolls the object equipment that reaches pulverizing, grinding, dispersion, emulsifying material, mainly by feed portion, discharging portion, rotating part, driving section (step-down gear, small transmission gear, motor, automatically controlled) form.
In a kind of preparation method of the poly-lactic acid material of printing for 3D, one or more in mineral wool, brucite fiber, calcium carbonate crystal whisker, polygorskite fiber are embraced in the sea that wherein said nano inorganic toughner is length-to-diameter ratio >=20:1, granularity≤10nm; Described dispersion agent is one or more in triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, guar gum.
The present invention adopts ultrasonic wave and coupling agent to carry out organic modification of surface processing to nano inorganic toughner, makes nano inorganic toughner in poly(lactic acid), have excellent stability and consistency; And adopt the technical matters of grinding, disperseing, mix, extruding, nano inorganic toughner can better be spread out in poly(lactic acid) system, use the poly(lactic acid) of the method modification not only to there is high excellent toughness and tensile strength, also do not affect the processing stability of poly(lactic acid) when 3D printing shaping, can in 3D printing technique, be widely used.
The outstanding feature of the present invention is:
1, the present invention adopts ultrasonic wave and coupling agent to carry out organic modification of surface processing to nano inorganic toughner, makes nano inorganic toughner in poly(lactic acid), have excellent stability and consistency.
2, the technical matters that the present invention adopts grinding, disperses, mixes, extrudes, nano inorganic toughner can better be spread out in poly(lactic acid) system and form the structure of homogeneous, during poly-lactic acid material printing shaping after modification, even, the cooling shrinking percentage of interiors of products stress distribution is identical, there is excellent forming stability, and toughness and tensile strength more excellent.
3, production process of the present invention is simple, easy to operate, is easy to suitability for industrialized production.
Embodiment
Below by embodiment, the present invention is described in further detail, but this should be interpreted as to scope of the present invention only limits to following example.In the situation that not departing from aforesaid method thought of the present invention, various replacements or the change according to ordinary skill knowledge and customary means, made, all should be within the scope of the present invention.
embodiment 1
1) titanate coupling agent of the nanometer sepiolite fibre of 10 weight parts, 0.5 weight part, appropriate deionized water are added to people in reactor, under the stirring velocity of the temperature of 60 ℃, 300r/min, with ultrasonication reaction 1h discharging, dry, grind and obtain the nano inorganic toughner that organic modification of surface is processed;
2) nano inorganic toughner and the poly(lactic acid) of 85 weight parts the organic modification of surface that obtains in step 1) processed be, the triethyl hexyl phosphoric acid of the fatty group dibasic acid of 3 weight parts, 3 weight parts joins in planetary ball mill, grinds, dispersion, combination treatment 1h discharging obtain mixture under the speed of 300r/min;
3) by step 2) in the twin screw extruder mixing extruding pelletization for compound that obtains, the time that material stops in forcing machine is 5 minutes.Double-screw extruder screw diameter is 75mm, and length-to-diameter ratio is 52:1, and extruder temperature is set as successively: 120 ℃, and 125 ℃, 135 ℃, 140 ℃, 145 ℃, 155 ℃ of die head temperatures;
4) by step 3) in institute granulation is dry at the temperature of 50 ℃ after 2 hours, with single screw extrusion machine, extrudes and be processed into the filament that diameter is 1.75mm, single screw extrusion machine screw diameter is 75mm, length-to-diameter ratio is 20:1, extruder temperature is set as successively: 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 155 ℃ of die head temperatures.
The PLA that twin-screw extrusion through single is mixed and modified detects contrast with the salient features through present method modification PLA later, and its comparison and detection result is as follows:
| Test item | Tradition modification PLA | Present method modification PLA | Pure PLA |
| Tensile strength (MPa) | 66 | 85 | 54 |
| Elongation at break (%) | 53 | 83 | 6 |
| Melt flow index (g/min) | 4.2 | 4.9 | 5.6 |
[0020] embodiment 2
1) the organic complex compound coupling agent of the nanometer brucite fiber of 25 weight parts, 2 weight parts, appropriate deionized water are added to people in reactor, under the stirring velocity of the temperature of 60 ℃, 200r/min, with ultrasonication reaction 2h discharging, dry, grind and obtain the nano inorganic toughner that organic modification of surface is processed;
2) nano inorganic toughner and the poly(lactic acid) of 60 weight parts the organic modification of surface that obtains in step 1) processed be, the sodium lauryl sulphate of the benzoic ether of 3 weight parts, 5 weight parts joins in planetary ball mill, grinds, dispersion, combination treatment 2h discharging obtain mixture under the speed of 400r/min;
3) by step 2) in the twin screw extruder mixing extruding pelletization for compound that obtains, the time that material stops in forcing machine is 6 minutes.Double-screw extruder screw diameter is 75mm, and length-to-diameter ratio is 20:1, and extruder temperature is set as successively: 120 ℃, and 125 ℃, 135 ℃, 140 ℃, 140 ℃, 145 ℃ of die head temperatures;
4) by step 3) in institute granulation is dry at the temperature of 50 ℃ after 2.5 hours, with single screw extrusion machine, extrudes and be processed into the filament that diameter is 1.75mm, single screw extrusion machine screw diameter is 75mm, length-to-diameter ratio is 20:1, extruder temperature is set as successively: 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 145 ℃ of die head temperatures.
The PLA that twin-screw extrusion through single is mixed and modified detects contrast with the salient features of process present method modification PLA later and pure PLA, and its comparison and detection result is as follows:
| Test item | Tradition modification PLA | Present method modification PLA | Pure PLA |
| Tensile strength (MPa) | 69 | 83 | 54 |
| Elongation at break (%) | 51 | 85 | 6 |
| Melt flow index (g/min) | 4.1 | 4.7 | 5.6 |
[0022] embodiment 3
1) the aluminic acid compound coupling agent of the nano-calcium carbonate calcium pyroborate of 15 weight parts, 1 weight part, appropriate deionized water are added to people in reactor, under the stirring velocity of the temperature of 60 ℃, 150r/min, with ultrasonication reaction 1h discharging, dry, grind and obtain the nano inorganic toughner that organic modification of surface is processed;
2) nano inorganic toughner and the poly(lactic acid) of 70 weight parts the organic modification of surface that obtains in step 1) processed be, the methyl amyl alcohol of the citrate of 2 weight parts, 2 weight parts joins in planetary ball mill, grinds, dispersion, combination treatment 1h discharging obtain mixture under the speed of 350r/min;
3) by step 2) in the twin screw extruder mixing extruding pelletization for compound that obtains, the time that material stops in forcing machine is 8 minutes.Double-screw extruder screw diameter is 75mm, and length-to-diameter ratio is 20:1, and extruder temperature is set as successively: 120 ℃, and 125 ℃, 130 ℃, 140 ℃, 145 ℃, 150 ℃ of die head temperatures;
4) by step 3) in institute granulation is dry at the temperature of 50 ℃ after 3 hours, with single screw extrusion machine, extrudes and be processed into the filament that diameter is 3mm, single screw extrusion machine screw diameter is 75mm, length-to-diameter ratio is 20:1, extruder temperature is set as successively: 125 ℃, 130 ℃, 135 ℃, 140 ℃, 140 ℃, 150 ℃ of die head temperatures.
The PLA that twin-screw extrusion through single is mixed and modified detects contrast with the salient features of process present method modification PLA later and pure PLA, and its comparison and detection result is as follows:
| Test item | Tradition modification PLA | Present method modification PLA | Pure PLA |
| Tensile strength (MPa) | 67 | 81 | 54 |
| Elongation at break (%) | 54 | 90 | 6 |
| Melt flow index (g/min) | 4.2 | 5.0 | 5.6 |
Claims (6)
1. a preparation method for the poly-lactic acid material of printing for 3D, is characterized in that concrete preparation method is as follows:
1) coupling agent of the nano inorganic toughner of 10-25 weight part, 0.5-2 weight part, appropriate solvent are added to people in reactor, under the stirring velocity of the temperature of 60 ℃, 100-300r/min, with ultrasonication reaction 1-3h discharging, dry, grind and obtain the nano inorganic toughner that organic modification of surface is processed;
2) nano inorganic toughner and the poly(lactic acid) of 60-85 weight part the organic modification of surface that obtains in step 1) processed be, the dispersion agent of the softening agent of 1-3 weight part, 1-5 weight part joins in planetary ball mill, grinds, dispersion, combination treatment 1-2h discharging obtain mixture under the speed of 300-450r/min;
3) by step 2) the twin screw extruder mixing extruding pelletization for mixture that obtains, the time that material stops in forcing machine is 5-8 minute;
4) by step 3) in institute granulation with single screw extrusion machine, extrude and be processed into the filament that diameter is 1.75mm, 3mm after being dried 2-3 hour with drying baker at the temperature of 50 ℃, diameter error is in 5%.
2. according to the preparation method of a kind of poly-lactic acid material of printing for 3D of the preparation described in claim 1, it is characterized in that described double-screw extruder screw diameter is 75mm, length-to-diameter ratio is 52:1, extruder temperature is set as successively: 120-125 ℃, 125-135 ℃, 135-145 ℃, 130-140 ℃, 135-140 ℃, die head temperature 145-155 ℃.
3. according to the preparation method of a kind of poly-lactic acid material of printing for 3D of the preparation described in claim 1, it is characterized in that described single screw extrusion machine screw diameter is 75mm, length-to-diameter ratio is 20:1, extruder temperature is set as successively: 125-135 ℃, 130-140 ℃, 135-145 ℃, 140-150 ℃, 145-155 ℃, die head temperature 145-155 ℃.
4. according to the preparation method of a kind of poly-lactic acid material of printing for 3D of the preparation described in claim 1, it is characterized in that described planetary ball mill is to utilize the rolling at a high speed in grinding pot of abrasive material and test portion, material is produced strong shear, impacts, rolls the object equipment that reaches pulverizing, grinding, dispersion, emulsifying material, mainly by feed portion, discharging portion, rotating part, driving section (step-down gear, small transmission gear, motor, automatically controlled) form.
5. according to the preparation method of a kind of poly-lactic acid material of printing for 3D described in claim 1, it is characterized in that nano inorganic toughner is that one or more in mineral wool, nanometer brucite fiber, nano-calcium carbonate calcium pyroborate, nanometer palygorskite fiber are embraced in nanometer sea; Described dispersion agent is one or more in triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, guar gum.
6. according to the preparation method of a kind of poly-lactic acid material of printing for 3D described in claim 1, the nano inorganic toughner described in it is characterized in that is that mineral wool, brucite fiber, calcium carbonate crystal whisker, polygorskite fiber are embraced in the sea of length-to-diameter ratio >=20:1, granularity≤10nm.
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| CN104177798A (en) * | 2014-09-19 | 2014-12-03 | 上海材料研究所 | Modified polylactic acid composite material suitable for 3D printing and preparation method of composite material |
| CN104312119A (en) * | 2014-11-06 | 2015-01-28 | 芜湖瀚博电子科技有限公司 | Straw 3D printing consumable and preparation method thereof |
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| WO2015168922A1 (en) * | 2014-05-09 | 2015-11-12 | Jf Polymers (Suzhou) Co. Ltd. | Highly crystalline poly (lactic acid) filaments for material- extrusion based additive manufacturing |
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| CN105462193A (en) * | 2014-09-03 | 2016-04-06 | 东北林业大学 | Whisker reinforced biodegradable polyester composite material and preparation method |
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| CN106893277A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of inorganics filled biodegradable 3D printing consumptive material and preparation method thereof |
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| CN105504713B (en) * | 2015-12-29 | 2017-07-14 | 广西三集科技有限公司 | A kind of 3D printing is material modified and preparation method thereof with polylactic acid microsphere |
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| CN106751379A (en) * | 2016-11-23 | 2017-05-31 | 中国科学院化学研究所 | Product prepared by a kind of fused glass pellet technique and preparation method thereof |
| CN107325504A (en) * | 2017-06-22 | 2017-11-07 | 清华大学 | A kind of 3 D-printing composite thermoelectric material |
| CN109337313A (en) * | 2018-09-12 | 2019-02-15 | 泉州市康馨化工科技有限公司 | The method for forming gradient composites using 3D printing |
| CN109291417A (en) * | 2018-09-14 | 2019-02-01 | 莱芜职业技术学院 | Novel degradable polylactic acid 3D printing material preparation method and application |
| CN110682512A (en) * | 2019-10-15 | 2020-01-14 | 武义斯汀纳睿三维科技有限公司 | Preparation method of enhanced 3D printing material |
| CN111500036A (en) * | 2020-05-15 | 2020-08-07 | 王智辉 | Heat-resistant high-strength 3D printing material and preparation method thereof |
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