CN110452508B - 一种用于3d打印柔性材料的制备技术 - Google Patents

一种用于3d打印柔性材料的制备技术 Download PDF

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CN110452508B
CN110452508B CN201810445512.7A CN201810445512A CN110452508B CN 110452508 B CN110452508 B CN 110452508B CN 201810445512 A CN201810445512 A CN 201810445512A CN 110452508 B CN110452508 B CN 110452508B
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万同
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Tianjin University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y70/00Materials specially adapted for additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids
    • C08K5/103Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/11Esters; Ether-esters of acyclic polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K

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Abstract

本发明设计了一种3D打印柔性材料的制备配方。该制备过程是:以柠檬酸苄酯,二丙二醇二苯甲酸酯,甘油三苯甲酸酯按照1.0~0.5∶1~2∶1.0~0.5比例混合。该混合物中加入乳酸铋5%,将真空干燥后的PLA与上述混合物按质量比85/15到60/40的范围进行混合,将得到的混合物在80℃的真空干燥箱中放置4h,使得增塑剂充分的渗入到PLA粒料中。然后用双螺杆对以上混合物进行熔融共混,双螺杆及喷嘴的温度分别设定为140℃、145℃、150℃以及150℃。该挤出粒料物是一种用于3D打印柔性材料。

Description

一种用于3D打印柔性材料的制备技术
技术领域
本发明涉及化学合成技术领域,具体涉及用于3D打印柔性材料助剂的制备技术。
背景技术
3D打印柔性材料具有很大的应用前景。目前聚乳酸材料的3D柔性材料的稳定性亟待开发,也是増塑改性研究的热点。目前已有多种无毒、环保增塑剂投入到工业化生产中,如柠檬酸酯类增塑剂、甘油酯类增塑剂、乙二醇的低聚物等。大量的研究表明这类增塑剂的増塑效果都比较好,但是这类增塑剂均因其分子量比较小而存在挥发性大、耐抽出性差和耐迁移性差等问题。增塑剂的挥发性大将导致增塑剂在与基体树脂进行熔融共混时不能完全进入到基体树脂的分子链间,起到増塑作用,不能很好的发挥其増塑效果;由于増塑材料可能在应用的过程中接触到水、油脂以及一些其他的有机溶剂,若增塑剂的耐抽出性太小,则会导致增塑剂的抽出,不仅使得材料的力学性能下降,如若被用于包装材料的増塑,还会污染被包装的物质;若增塑剂的耐迁移性太差,不能长期稳定的存在于材料中,随着增塑材料放置时间的延长,增塑剂将会迁至材料的表面,引起増塑材料性能的衰减,加速增塑材料的老化,降低材料的使用寿命。上述助剂很难满足和制备3D打印柔性材料。
发明内容
本专利是利用柠檬酸苄酯,二丙二醇二苯甲酸酯,甘油三苯甲酸酯形成混合助剂保持了聚酯类增塑剂结构特性的基础上引入了醚键,提高增塑剂的分子质量。加入乳酸铋可以有效提高柔性材料稳定性。通过共混挤出方式加入PLA中进行改性,有效的改善PLA柔韧性,是一种用于3D打印柔性材料。
用于3D打印柔性材料的制备技术包括如下步骤:
1)将柠檬酸苄酯,二丙二醇二苯甲酸酯,甘油三苯甲酸酯以摩尔比为1.0~0.5∶1~2∶1.0~0.5的比例混合。
2)将该混合物中加入乳酸铋5~10%,将真空干燥后的PLA与上述混合物按质量比85/15到60/40的范围进行混合,将得到的混合物在80℃的真空干燥箱中放置4h,使得增塑剂充分的渗入到PLA粒料中。
3)用双螺杆对以上混合物进行熔融共混,双螺杆及喷嘴的温度分别设定为140℃、145℃、150℃以及150℃。该挤出粒料物是一种用于3D打印柔性材料。
本发明的有益效果是:
本发明提出的柠檬酸苄酯,二丙二醇二苯甲酸酯,甘油三苯甲酸酯形成混合助剂的结构特性中引入了酯和醚键结构,混合助剂的分子有苯环结构,同时加入乳酸铋,这些都可以有效提高柔性材料稳定性。它是一种3D打印柔性材料。
具体实施方式
下面结合具体的实施例对本发明进行进一步的说明。
实施例1:3D打印柔性材料的制备:
1)将柠檬酸苄酯1.0mol,二丙二醇二苯甲酸酯2mol,甘油三苯甲酸酯0.5mol混合。
2)将该混合物中加入乳酸铋5~10%,将真空干燥后的PLA与上述混合物按质量比80/20进行混合,将得到的混合物在80℃的真空干燥箱中放置4h,使得增塑剂充分的渗入到PLA粒料中。
3)用双螺杆对以上混合物进行熔融共混,双螺杆及喷嘴的温度分别设定为140℃、145℃、150℃以及150℃。该挤出线材物是一种用于3D打印柔性材料。
经过3D打印后,材料的断裂伸长率达到500%,放置100天后无明显变化。

Claims (1)

1.一种3D打印柔性材料的制备方法,其特征在于:
柔性材料由聚乳酸、柠檬酸苄酯、二丙二醇二苯甲酸酯、甘油三苯甲酸酯、乳酸铋组成;
1)将柠檬酸苄酯,二丙二醇二苯甲酸酯,甘油三苯甲酸酯以摩尔比为1.0~0.5∶1~2∶1.0~0.5的比例混合;
2)将该混合物中加入乳酸铋5~10%,将真空干燥后的PLA与上述混合物按质量比85/15到80/20的范围进行混合,将得到的混合物在80℃的真空干燥箱中放置4h,使得增塑剂充分的渗入到PLA粒料中;
3)用双螺杆对以上混合物进行熔融共混,双螺杆及喷嘴的温度分别设定为140℃、145℃、150℃以及150℃;该挤出粒料物是一种用于3D打印柔性材料。
CN201810445512.7A 2018-05-07 2018-05-07 一种用于3d打印柔性材料的制备技术 Active CN110452508B (zh)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090155326A1 (en) * 2007-11-12 2009-06-18 Mack Brendan C Layered drug delivery polymer monofilament fibers
CN106278881A (zh) * 2015-05-19 2017-01-04 天津科技大学 一种用于3d打印柔性材料助剂的合成方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090155326A1 (en) * 2007-11-12 2009-06-18 Mack Brendan C Layered drug delivery polymer monofilament fibers
CN106278881A (zh) * 2015-05-19 2017-01-04 天津科技大学 一种用于3d打印柔性材料助剂的合成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
新型増塑剂的制备及其对PLA増塑效果的研究;杨光瑞;《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》;20170215(第2期);正文第15-18页 *

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