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WO2019085522A1 - Matériau d'impression 3d d'acide polylactique et fil préparé à partir de celui-ci - Google Patents

Matériau d'impression 3d d'acide polylactique et fil préparé à partir de celui-ci Download PDF

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Publication number
WO2019085522A1
WO2019085522A1 PCT/CN2018/092799 CN2018092799W WO2019085522A1 WO 2019085522 A1 WO2019085522 A1 WO 2019085522A1 CN 2018092799 W CN2018092799 W CN 2018092799W WO 2019085522 A1 WO2019085522 A1 WO 2019085522A1
Authority
WO
WIPO (PCT)
Prior art keywords
polylactic acid
printing material
average molecular
molecular weight
wire
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/092799
Other languages
English (en)
Chinese (zh)
Inventor
熊凯
袁志敏
蔡彤旻
黄险波
曾祥斌
焦建
卢昌利
杨晖
麦开锦
董学腾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Original Assignee
ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ZHUHAI WANGO CHEMICAL CO Ltd, Kingfa Science and Technology Co Ltd, Shanghai Kingfa Science and Technology Co Ltd filed Critical ZHUHAI WANGO CHEMICAL CO Ltd
Publication of WO2019085522A1 publication Critical patent/WO2019085522A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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

Definitions

  • the invention belongs to the technical field of polymer materials, and in particular relates to a polylactic acid 3D printing material and a wire prepared therefrom.
  • the starch-rich corn can be produced by modern biotechnology to produce a colorless and transparent liquid-lactic acid, which is then subjected to a special polymerization process to form a granular polymer material, polylactic acid (PLA).
  • PLA has the best tensile strength and elongation and can be produced by various common processing methods, such as: melt extrusion, injection molding, blown film forming, foam molding and vacuum forming.
  • PLA plastic can be used in 3D printing materials, but at this stage, PLA is also limited as a general-purpose plastic, especially 3D printing consumable substrate.
  • the notched impact strength is less than 3KJ/m 2 , which severely limits its wide application. 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.
  • Patent application No.: 201510069937.9 discloses a 3D printing PLA consumable and a preparation method thereof, which are made of the following raw materials by weight: PLA plastic 99.3-99.7%, pigment 0.1-0.3%, auxiliary agent 0.2-0.4 %, but not mentioned for wire extrusion stability.
  • the invention further finds that when the structure of the polylactic acid 3D printing material satisfies the following relationship: 0.8 ⁇ Mx/Dx ⁇ 7, the extrusion speed of the polylactic acid 3D printing material is 45Kg/h, and the wire diameter of the extruded wire When it is 1.75cm, the wire diameter difference is ⁇ 0.12cm, and the wire diameter deviation is ⁇ 5%, which shows better wire extrusion stability.
  • a primary object of the present invention is to provide a polylactic acid 3D printing material having significantly improved extrusion stability.
  • Another object of the present invention is to provide a wire material prepared from the above polylactic acid 3D printing material.
  • a polylactic acid 3D printing material in parts by weight, comprising the following components:
  • the number average molecular weight Mn of the polylactic acid is 50,000 to 150,000;
  • the structure of the polylactic acid 3D printed material satisfies the following relationship:
  • Dx represents a polydispersity coefficient, defined as Mw/Mn, wherein Mw is the weight average molecular weight of the polylactic acid 3D printing material, Mn is the number average molecular weight of the polylactic acid 3D printing material, and Mx represents the polylactic acid 3D printing material at 190 ° C
  • Mw is the weight average molecular weight of the polylactic acid 3D printing material
  • Mn is the number average molecular weight of the polylactic acid 3D printing material
  • Mx represents the polylactic acid 3D printing material at 190 ° C
  • the method for testing the weight average molecular weight Mw and the number average molecular weight Mn of the polylactic acid 3D printing material is: using a Waters 2410 gel permeation chromatograph of Waters Corporation of the United States, the column temperature is 25 ° C, tetrahydrofuran is a solvent and a leaching phase. The flow rate was 1.0 ml/min and the retention time was 50 min. The polystyrene standards with different molecular weights were used as calibration curves.
  • Mx/Dx refers to the ratio of the melt flow rate of the molecular structure to the polydispersity coefficient, which actually reflects the processing window width and extrusion stability of the polylactic acid 3D printing material, and there are many factors affecting the ratio of Mx/Dx.
  • the microstructure of the raw material polylactic acid is different, and it is well known to those skilled in the art that the polylactic acid can be directly polycondensed by L-lactic acid, D-lactic acid monomer or by ring-opening polymerization of lactide, and the L-lactic acid is adjusted during the synthesis.
  • the content of D-lactic acid monomer also affects the molecular weight of the synthesized polylactic acid and the molecular chain sequence structure, thereby making the microstructure of polylactic acid different.
  • the addition of the auxiliary components and the preparation process (such as different process parameters) and other factors will affect the molecular structure of the final prepared polylactic acid 3D printed material, which leads to its Mx/Dx There is a significant difference in the ratio.
  • the invention finds that when the structure of the polylactic acid 3D printing material satisfies the following relationship: 0.8 ⁇ Mx/Dx ⁇ 7, when the drawing speed of the drawing wire is 45Kg/h, and the wire diameter of the extruded wire is 1.75cm, the wire line The diameter difference is ⁇ 0.12cm, and the relative deviation of the wire diameter is ⁇ 5%, thereby exhibiting good extrusion stability.
  • the structure of the polylactic acid 3D printing material satisfies the following relationship:
  • the structure of the polylactic acid 3D printing material satisfies the following relationship:
  • Dx represents a polydispersity coefficient, defined as Mw/Mn, wherein Mw is the weight average molecular weight of the polylactic acid 3D printing material, Mn is the number average molecular weight of the polylactic acid 3D printing material, and Mx represents the polylactic acid 3D printing material at 190 ° C
  • Mw is the weight average molecular weight of the polylactic acid 3D printing material
  • Mn is the number average molecular weight of the polylactic acid 3D printing material
  • Mx represents the polylactic acid 3D printing material at 190 ° C
  • the polylactic acid has a number average molecular weight Mn of from 60,000 to 130,000. If the molecular weight is too low, the wire diameter stability during extrusion processing is deteriorated.
  • the processing aid is selected from the group consisting of a hard ester amide, an oleic acid amide, an erucamide, a zinc stearate, a polymer complex ester of a metal soap, an ethylene bis stearamide, a polyethylene wax, and a silicone lubricant.
  • a hard ester amide an oleic acid amide, an erucamide, a zinc stearate, a polymer complex ester of a metal soap, an ethylene bis stearamide, a polyethylene wax, and a silicone lubricant.
  • the present invention also provides a polylactic acid 3D printing wire which is prepared from the above polylactic acid 3D printing material.
  • the invention has the following beneficial effects:
  • the invention finds that when the structure of the polylactic acid 3D printing material satisfies the following relationship: 0.8 ⁇ Mx/Dx ⁇ 7, the extrusion speed of the polylactic acid 3D printing material is 45Kg/h, and the wire diameter of the extruded wire is At 1.75cm, the wire diameter difference is ⁇ 0.12cm, and the wire diameter deviation is ⁇ 5%, which shows good wire extrusion stability.
  • the raw materials used in the present invention are as follows:
  • Polylactic acid (PLA1) homemade, the number average molecular weight Mn is 90,000;
  • Polylactic acid (PLA2) homemade, the number average molecular weight Mn is 55000;
  • Polylactic acid (PLA3) homemade, the number average molecular weight Mn is 40,000;
  • Processing aids polymer complex esters of metal soap, ethylene bis stearamide, and silicone masterbatch are all derived from commercially available products.
  • the preparation method of polylactic acid is as follows:
  • a certain amount of the lactide product prepared in Table 1 was accurately weighed into a sealed tube, and a certain amount of a solution of stannous isooctanoate in methylene chloride was added thereto, and the solvent dichloromethane was distilled off at room temperature.
  • the tube was placed at room temperature, evacuated, and high purity nitrogen was injected and repeated three times. After evacuating for half an hour under a certain degree of vacuum, the polymerization tube was vacuum-sealed. After the polymerization tube is sealed, the monomer is first melted, shaken vigorously, the monomer is mixed with the catalyst, and polymerization is carried out at a given temperature.
  • the sealed tube was taken out, cooled to room temperature, and the sealed tube was broken to obtain a polymer solid.
  • the polymer solid was dissolved under reflux with 5% (w/w) chloroform, and the solution was filtered, and then precipitated with 5 times the volume of chloroform in methanol to obtain a white floc. After suction filtration, the product was vacuum dried at 70 ° C until use.
  • the composition of the raw material of the polylactic acid preparation reactant is as shown in Table 2.
  • the PLA and the processing aid are uniformly mixed according to the parts by weight shown in Table 3, and then put into a twin-screw extruder, extruded at 160 ° C - 180 ° C, and granulated to obtain a polylactic acid 3D printing material;
  • the polylactic acid 3D printing material is drawn on a single-screw extruder, the single-screw extrusion temperature is controlled from 160 ° C to 210 ° C, and the temperature of the control water tank is between 40 ° C and 60 ° C, thereby obtaining a polylactic acid 3D printing wire material, wherein
  • the wire diameter of the extruded wire was 1.75 cm, and the extrusion speed of the wire was 45 Kg/h.
  • the performance test results are shown in Table 1.
  • Comparative Example 1 The number average molecular weight Mn of polylactic acid was 40,000, and the rest was the same as in Example 2.
  • Mw is the weight average molecular weight of the polylactic acid 3D printing material
  • Mn is the number average molecular weight of the polylactic acid 3D printing material: analyzed by Waters 2410 gel permeation chromatograph of Waters, USA, column temperature 25 ° C, tetrahydrofuran as solvent and leaching phase The flow rate was 1.0 ml/min and the retention time was 50 min. The polystyrene standards with different molecular weights were used as calibration curves.
  • Mx represents the melt flow rate of the polylactic acid 3D printed material at 190 ° C under a load of 2.16 kg, measured according to the ISO 1133 standard.
  • Test method for extremely poor wire diameter Tested with vernier caliper, the wire diameter difference is the difference between the maximum value and the minimum value of a set of measured values; the larger the wire diameter extreme difference, the worse the extrusion stability of the wire;
  • Relative deviation of wire diameter refers to the percentage of absolute deviation of a certain measurement as the average value.
  • the absolute deviation refers to the difference between the measured value and the average value. The larger the relative deviation of the wire diameter, the extrusion stability of the wire. The worse.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)

Abstract

L'invention concerne un matériau d'impression 3D d'acide polylactique et un fil préparé à partir de celui-ci. Le matériau d'impression 3D d'acide polylactique comprend les constituants suivants : (a) 98,0 à 100 parties d'acide polylactique ; et (b) 0 à 2,0 parties d'un auxiliaire de traitement, la masse moléculaire moyenne en nombre Mn de l'acide polylactique étant de 50 000 à 150 000 sur la base du poids total de la totalité de l'acide polylactique. La structure du matériau d'impression 3D d'acide polylactique satisfait la relation suivante : 0,8 ≤ Mx / Dx ≤ 7, Dx représentant un coefficient de polydispersité défini comme Mw/Mn, Mw étant la masse moléculaire moyenne en poids du matériau d'impression 3D d'acide polylactique, Mn étant la masse moléculaire moyenne en nombre du matériau d'impression 3D d'acide polylactique, et Mx représentant un indice de fluidité du matériau d'impression 3D d'acide polylactique à une température de 190 °C sous une charge de 2,16 kg. Lorsque la structure satisfait la relation ci-dessus, le matériau d'impression 3D d'acide polylactique présente une plage de diamètre de fil ≤ 0,12 cm et un écart relatif de diamètre de fil < 5 % lorsqu'une vitesse d'extrusion par traction est de 45 kg/h et un diamètre de fil extrudé est de 1,75 cm, présentant ainsi une excellente stabilité d'extrusion de fil.
PCT/CN2018/092799 2017-11-03 2018-06-26 Matériau d'impression 3d d'acide polylactique et fil préparé à partir de celui-ci Ceased WO2019085522A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201711069835.2A CN107974062B (zh) 2017-11-03 2017-11-03 一种聚乳酸3d打印材料和由其制备的线材
CN201711069835.2 2017-11-03

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WO2019085522A1 true WO2019085522A1 (fr) 2019-05-09

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107974062B (zh) * 2017-11-03 2020-10-09 金发科技股份有限公司 一种聚乳酸3d打印材料和由其制备的线材
CN107936502A (zh) * 2017-11-03 2018-04-20 金发科技股份有限公司 一种聚乳酸3d打印材料和由其制备的线材
CN109608841A (zh) * 2018-12-12 2019-04-12 广安长明高端产业技术研究院 一种MXene增强聚乳酸3D打印材料的制备方法及产品

Citations (7)

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US5880254A (en) * 1995-07-25 1999-03-09 Shimadzu Corporation Method for producing polylactic acid and apparatus used therefor
WO2004048471A1 (fr) * 2002-11-25 2004-06-10 Daicel Chemical Industries, Ltd. Composition de resine biodegradable
WO2005061617A1 (fr) * 2003-12-23 2005-07-07 Smith & Nephew, Plc Polyacetal segmente reglable
CN101563391A (zh) * 2006-12-15 2009-10-21 金伯利-克拉克环球有限公司 用于形成纤维的生物可降解聚乳酸
CN101921371A (zh) * 2009-06-09 2010-12-22 中国科学院化学研究所 一种长链支化聚乳酸树脂及其制备方法
CN102010583A (zh) * 2010-10-15 2011-04-13 浙江大学 高分子量长链支化结晶性聚乳酸材料及其制备方法
CN107974062A (zh) * 2017-11-03 2018-05-01 金发科技股份有限公司 一种聚乳酸3d打印材料和由其制备的线材

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CN101362853B (zh) * 2008-09-12 2011-03-30 浙江海正生物材料股份有限公司 一种低成本全生物降解聚乳酸片材及其制备方法
SG187786A1 (en) * 2010-08-12 2013-03-28 Univ Nanyang Tech A biodegradable ocular implant
CN102408553B (zh) * 2011-09-15 2013-05-08 南开大学 医用生物降解性聚乳酸-谷氨酸的合成工艺
KR101476378B1 (ko) * 2012-09-19 2014-12-24 주식회사 엘지화학 변성 폴리락타이드 수지 및 그 제조방법
CN104845300B (zh) * 2015-03-26 2016-08-17 成都新柯力化工科技有限公司 一种用于三维打印的聚乳酸复合材料及其制备方法
CN106893275A (zh) * 2015-12-18 2017-06-27 四川鑫达企业集团有限公司 一种可降解回收聚乳酸材料及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5880254A (en) * 1995-07-25 1999-03-09 Shimadzu Corporation Method for producing polylactic acid and apparatus used therefor
WO2004048471A1 (fr) * 2002-11-25 2004-06-10 Daicel Chemical Industries, Ltd. Composition de resine biodegradable
WO2005061617A1 (fr) * 2003-12-23 2005-07-07 Smith & Nephew, Plc Polyacetal segmente reglable
CN101563391A (zh) * 2006-12-15 2009-10-21 金伯利-克拉克环球有限公司 用于形成纤维的生物可降解聚乳酸
CN101921371A (zh) * 2009-06-09 2010-12-22 中国科学院化学研究所 一种长链支化聚乳酸树脂及其制备方法
CN102010583A (zh) * 2010-10-15 2011-04-13 浙江大学 高分子量长链支化结晶性聚乳酸材料及其制备方法
CN107974062A (zh) * 2017-11-03 2018-05-01 金发科技股份有限公司 一种聚乳酸3d打印材料和由其制备的线材

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CN107974062A (zh) 2018-05-01

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