WO2019085523A1 - 一种聚乳酸3d打印材料和由其制备的线材 - Google Patents

一种聚乳酸3d打印材料和由其制备的线材 Download PDF

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Publication number
WO2019085523A1
WO2019085523A1 PCT/CN2018/092801 CN2018092801W WO2019085523A1 WO 2019085523 A1 WO2019085523 A1 WO 2019085523A1 CN 2018092801 W CN2018092801 W CN 2018092801W WO 2019085523 A1 WO2019085523 A1 WO 2019085523A1
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polylactic acid
printing material
temperature
wire
wire diameter
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PCT/CN2018/092801
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English (en)
French (fr)
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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
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金发科技股份有限公司
珠海万通化工有限公司
上海金发科技发展有限公司
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Publication of WO2019085523A1 publication Critical patent/WO2019085523A1/zh

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides

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 ° C ⁇ Tx - Ty ⁇ 60 ° C, the polylactic acid 3D printing material has a drawing speed of 45 Kg / h at the drawing, and the extruded wire When the wire diameter 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 weight content of the right-handed body of the polylactic acid is 0.3% to 5%;
  • Test method for the right-handed body of polylactic acid 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 complexing ability of the two enantiomers of lactic acid is different. , thereby making it easy to separate the gas chromatograph, using this method to obtain the percentage of the two enantiomers in the polylactic acid;
  • the structure of the polylactic acid 3D printed material satisfies the following relationship:
  • Tx is the maximum weight loss rate temperature of polylactic acid 3D printing material
  • Ty is the extrapolated initial decomposition temperature of polylactic acid 3D printing material
  • the test method of the maximum weight loss rate temperature Tx and the extrapolation initial decomposition temperature Ty of the polylactic acid 3D printing material is: using NETZCH TG209 type thermogravimetric analyzer to measure the thermal weight loss of the polylactic acid 3D printing material under a nitrogen atmosphere
  • the DTG curve and the TG curve, the peak top temperature of the DTG curve is the maximum weight loss rate temperature Tx, and the intersection of the tangent to the baseline of the falling portion of the TG curve is the extrapolated initial decomposition temperature Ty; the heating rate is selected to be 10 ° C / min.
  • Tx refers to the maximum weight loss rate temperature, which reflects the turning point temperature of the falling section of the weight loss curve.
  • Ty refers to the extrapolated initial decomposition temperature, which reflects the temperature at which the material begins to decompose;
  • Tx-Ty refers to the maximum weight loss rate temperature of the molecular structure.
  • polylactic acid can be directly polycondensed by L-lactic acid, D-lactic acid monomer or by ring-opening polymerization of lactide, and the content of L-lactic acid and D-lactic acid monomer can be adjusted during the synthesis. Or by controlling the amount of catalyst added, adjusting the degree of vacuum and the reaction time, the molecular weight of the synthesized polylactic acid and the molecular chain sequence structure are also affected, so that the microstructure of the polylactic acid is different. In 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 Tx-Ty There is a significant difference in the difference.
  • the invention finds that when the structure of the polylactic acid 3D printing material satisfies the following relationship: 0 ° C ⁇ Tx - Ty ⁇ 60 ° C, when the drawing speed of the drawing wire is 45 Kg / h, and the wire diameter of the extruded wire is 1.75 cm, The wire diameter difference is ⁇ 0.12cm, and the wire diameter deviation is ⁇ 5%, which shows 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:
  • Tx is the maximum weight loss rate temperature of polylactic acid 3D printing material
  • Ty is the extrapolated initial decomposition temperature of polylactic acid 3D printing material
  • the polylactic acid has a weight content of the right-handed body of 0.5% to 3% based on the total weight of the entire polylactic acid. If the content of the right-handed body is too high, the crystallization rate of the polylactic acid becomes slow, and the wire diameter stability deteriorates during extrusion processing.
  • 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 out that when the structure of the polylactic acid 3D printing material satisfies the following relationship: 0 ° C ⁇ Tx - Ty ⁇ 60 ° C, the polylactic acid 3D printing material has a drawing speed of 45 Kg / h at the drawing line, and the extruded wire line When the diameter is 1.75 cm, the wire diameter difference is ⁇ 0.12 cm, and the wire diameter deviation is ⁇ 5%, thereby exhibiting good wire extrusion stability.
  • the raw materials used in the present invention are as follows:
  • Polylactic acid (PLA1) self-made, the weight content of the right-handed body is 2%;
  • Polylactic acid (PLA2) self-made, the weight content of the right-handed body is 4%;
  • Polylactic acid (PLA3) self-made, the weight content of the right-handed body is 6%;
  • 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 obtained in the step (1) is drawn on a single-screw extruder, and 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 to obtain polylactic acid.
  • Comparative Example 1 The weight content of the right-handed body of polylactic acid was 6%, and the rest was the same as in Example 2.
  • Test method for maximum weight loss rate temperature (Tx) and extrapolated initial decomposition temperature (Ty) of polylactic acid 3D printing materials The weight loss DTG curve of the resin was measured under a nitrogen atmosphere using NETZCH TG209 thermogravimetric analyzer. In the TG curve, the peak top temperature of the DTG curve is the maximum weight loss rate temperature Tx, and the intersection of the tangent to the baseline of the falling portion of the TG curve is the extrapolated initial decomposition temperature Ty; the heating rate is selected to be 10 ° C / min.
  • Test method for the right-handed body of polylactic acid 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 complexing ability of the two enantiomers of lactic acid is different.
  • the percentage of the two enantiomers in the polylactic acid is obtained by the method. The specific steps are as follows: preparing a standard solution having a known content of the right-handed body, and recording the standard solution in the chromatogram.
  • Peak time according to the concentration and peak area of the standard sample, the standard curve equation is obtained; then the sample chromatogram under the same chromatographic conditions is compared with the polylactic acid standard solution spectrum, and the L-lactic acid and D in the sample are determined according to the retention time.
  • - Lactic acid quantified by an external standard method to calculate the content of D-lactic acid in the sample, that is, the content of the right-handed body.
  • 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.

Abstract

本发明公开了一种聚乳酸3D打印材料和由其制备的线材，包括如下组分: (a)聚乳酸 98.0～100份； (b)加工助剂 0～2.0份；其中，基于整个聚乳酸的总重量，所述聚乳酸的右旋体的重量含量为0.3％～5％；该聚乳酸3D打印材料的结构满足如下关系式： 0℃≤Tx-Ty≤60℃, 其中，Tx是聚乳酸3D打印材料的最大失重速率温度，Ty是聚乳酸3D打印材料的外推起始分解温度。本发明通过研究发现，当聚乳酸3D打印材料的结构满足如下关系式：0℃≤Tx-Ty≤60℃时，该聚乳酸3D打印材料在拉线挤出速度为45Kg/h，挤出线材线径为1.75cm时，线材线径极差≤0.12cm，线材线径相对偏差<5％，从而展现出良好的线材挤出稳定性。

Description

一种聚乳酸3D打印材料和由其制备的线材 技术领域
本发明属于高分子材料技术领域，具体涉及一种聚乳酸3D打印材料和由其制备的线材。
背景技术
饱含淀粉质的玉米经过现代生物技术可生产出无色透明的液体-乳酸，再经过特殊的聚合反应过程生成颗粒状高分子材料—聚乳酸(PLA)。PLA具有最良好的抗拉强度及延展度，可以用各种普通加工方式生产，例如：熔化挤出成型，注射成型，吹膜成型，发泡成型及真空成型等。另外，由于PLA具有良好的生物降解性，因此，PLA塑料可被应用于3D打印材料中，但现阶段将PLA作为通用塑料特别是3D打印耗材基材大面积推广应用还受到一定的限制，这主要是由于聚乳酸的脆性严重，缺口冲击强度小于3KJ/m 2，严重的限制了它的广泛应用。因此如何使聚乳酸的韧性得到提高而又不影响其挤出稳定性是扩大聚乳酸在3D打印耗材中的应用中必须解决的问题。
专利申请号：201510069937.9公开了一种3D打印PLA耗材及其制备方法，该3D打印PLA耗材按重量百分比由下列原料制成：PLA塑料99.3-99.7％、颜料0.1-0.3％、助剂0.2-0.4％，但是对于线材挤出稳定性未提及。
本发明通过研究进一步发现，当聚乳酸3D打印材料的结构满足如下关系式：0℃≤Tx-Ty≤60℃时，该聚乳酸3D打印材料在拉线挤出速度为45Kg/h，挤出线材线径为1.75cm时，线材线径极差≤0.12cm，线材线径相对偏差<5％，从而展示出较好的线材挤出稳定性。
发明内容
本发明的首要目的在于提供一种聚乳酸3D打印材料，该聚乳酸3D打印材料具有明显改善的挤出稳定性。
本发明的另一目的在于提供由上述聚乳酸3D打印材料制备得到的线材。
本发明是通过以下技术方案实现的：
一种聚乳酸3D打印材料，按重量份数计，包括如下组分:
(a)聚乳酸     98.0～100份；
(b)加工助剂   0～2.0份；
其中，基于整个聚乳酸的总重量，所述聚乳酸的右旋体的重量含量为0.3％～5％；
聚乳酸的右旋体的的测试方法：采用安捷伦HP6890气相色谱仪，利用气相色谱柱中环糊精的分子形成的配合物有不同的平衡常数，对乳酸的两种对映体的络合能力不同，从而使其简便的气相色谱分离，用这种方法得到两种对映体在聚乳酸中的百分比；
该聚乳酸3D打印材料的结构满足如下关系式：
0℃≤Tx-Ty≤60℃,
其中，Tx是聚乳酸3D打印材料的最大失重速率温度，Ty是聚乳酸3D打印材料的外推起始分解温度。
其中，所述聚乳酸3D打印材料最大失重速率温度Tx和外推起始分解温度Ty的测试方法：采用NETZCH公司的TG209型热重分析仪，在氮气气氛下测定聚乳酸3D打印材料的热失重DTG曲线和TG曲线，DTG曲线的峰顶温度为最大失重速率温度Tx,TG曲线下降段的切线与基线的交点为外推起始分解温度Ty；选择升温速率为10℃/min。
Tx是指最大失重速率温度，反映的是失重曲线下降段的转折点温度，Ty是指外推起始分解温度，反映的是材料开始分解的温度；Tx-Ty是指分子结构的最大失重速率温度与外推起始分解温度的差值，其实际反映的是聚乳酸3D打印材料的加工窗口宽窄及挤出稳定性，影响Tx-Ty的差值的因素有很多，比如原料聚乳酸的微观结构不同，本领域技术人员公知，聚乳酸可以通过L-乳酸、D-乳酸单体直接缩聚或者通过丙交酯开环聚合得到，合成过程中，通过调整L-乳酸和D-乳酸单体的含量，或者通过控制催化剂的加入量，调整真空度以及反应时间，也会对合成的聚乳酸的分子量和分子链序列结构产生影响，从而使聚乳酸的微观结构不同。另外，加入的助剂组分及制备工艺过程(如工艺参数的不同等)等诸多因素，都会影响最终制备得到的聚乳酸3D打印材料的分子结构存在较大区别，从而导致其Tx-Ty的差值存在明显差异。
本发明通过研究发现，当聚乳酸3D打印材料的结构满足如下关系式：0℃≤Tx-Ty≤60℃时，在拉线挤出速度为45Kg/h，挤出线材线径为1.75cm时，线材线径极差≤0.12cm，线材线径相对偏差<5％，从而展现出良好的挤出稳定性。
优选的，所述聚乳酸3D打印材料的结构满足如下关系式：
5℃≤Tx-Ty≤50℃,
更优选的，所述聚乳酸3D打印材料的结构满足如下关系式：
10℃≤Tx-Ty≤40℃,
其中，Tx是聚乳酸3D打印材料的最大失重速率温度，Ty是聚乳酸3D打印材料的外推起始分解温度。
优选的，基于整个聚乳酸的总重量，所述聚乳酸的右旋体的重量含量为0.5％～3％。若右旋体含量过高，聚乳酸结晶速率变慢，挤出加工时线径稳定性变差。
所述加工助剂选自硬酯酰胺、油酸酰胺、芥酸酰胺、硬脂酸锌、金属皂的高分子复合酯、乙撑双硬脂酰胺、聚乙烯蜡、硅酮类润滑剂中的一种或两种以上的混合物。
本发明还提供一种聚乳酸3D打印线材，由上述的聚乳酸3D打印材料制备得到。
本发明与现有技术相比，具有如下有益效果：
本发明通过研究发现，当聚乳酸3D打印材料的结构满足如下关系式：0℃≤Tx-Ty≤60℃时，该聚乳酸3D打印材料在拉线挤出速度为45Kg/h，挤出线材线径为1.75cm时，线材线径极差≤0.12cm，线材线径相对偏差<5％，从而展现出良好的线材挤出稳定性。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
本发明所采用的原料如下：
聚乳酸(PLA1)：自制，右旋体的重量含量为2％；
聚乳酸(PLA2)：自制，右旋体的重量含量为4％；
聚乳酸(PLA3)：自制，右旋体的重量含量为6％；
加工助剂：金属皂的高分子复合酯、乙撑双硬脂酰胺、硅酮母粒均来源于市购产品。
聚乳酸的制备方法如下：
在反应容器中加入如表1比例的的L-乳酸、D-乳酸单体和ZnO，搅拌均匀，于80-140℃温度和4-10KPa压力下反应6-12h，蒸出水，生成低聚物。反应产物于减压蒸馏反应容器中加入ZSM-5型分子筛，搅拌均匀，在170-210℃和102-103Pa压力下减压蒸馏，至无产品馏出，时间为7-15h，得丙交酯产品。
表1 反应物原料组成比
Figure PCTCN2018092801-appb-000001
精确称取一定量的表1制备的的丙交酯产品于封管中，再加入一定量的异辛酸亚锡二氯甲烷溶液，在室温下抽去溶剂二氯甲烷。将封管置于室温下，抽空，注入高纯氮，重复三次。于 一定真空度下抽空半小时后，将聚合管真空下封口。聚合管封口后，先加热单体熔化，用力摇匀，使单体与催化剂混匀，再在给定的温度下进行聚合。反应一定时间后，取出封管，冷至室温，打破封管得到聚合物固体。将聚合物固体用5％(W/W)的氯仿回流溶解，溶液过滤后，用5倍于氯仿体积的甲醇进行沉淀，得白色絮状沉淀。抽滤后将产品在70℃下真空干燥备用。聚乳酸制备反应物原料组成比如表2。
表2 反应物原料组成比
Figure PCTCN2018092801-appb-000002
实施例1-6：聚乳酸3D打印材料的制备
将PLA和加工助剂按表3所示重量份数混合均匀后投入双螺杆挤出机中，于160℃-180℃挤出、造粒，得到聚乳酸3D打印材料；
将步骤(1)得到的聚乳酸3D打印材料在单螺杆挤出机上进行拉线，控制单螺杆挤出温度为160℃-210℃，控制水槽温度为40℃～60℃之间，即得聚乳酸3D打印线材，其中，挤出线材线径为1.75cm，拉线挤出速度为45Kg/h，性能测试结果如表1所示。
对比例1：聚乳酸的右旋体的重量含量为6％，其余同实施例2。
性能测试方法：
聚乳酸3D打印材料的最大失重速率温度(Tx)和外推起始分解温度(Ty)的测试方法：采用NETZCH公司的TG209型热重分析仪，在氮气气氛下测定树脂的热失重DTG曲线和TG曲线，DTG曲线的峰顶温度为最大失重速率温度Tx,TG曲线下降段的切线与基线的交点为外推起始分解温度Ty；选择升温速率为10℃/min。
聚乳酸的右旋体的的测试方法：采用安捷伦HP6890气相色谱仪，利用气相色谱柱中环糊精的分子形成的配合物有不同的平衡常数，对乳酸的两种对映体的络合能力不同，从而使其简便的气相色谱分离，用这种方法得到两种对映体在聚乳酸中的百分比，具体步骤如下：配制右旋体含量已知的标准溶液，记录色谱图中的标准溶液的出峰时间；根据标准样品的浓度和峰面积，得到标准曲线方程；再将相同色谱条件下的样品色谱图与聚乳酸标准液谱图进行对照，根据保留时间确定样品中的L-乳酸、D-乳酸；用外标法定量，计算出样品中D- 乳酸的含量即右旋体含量。
线径极差的测试方法：用游标卡尺测试，线径极差是指一组测量值内最大值与最小值之差；线径极差值越大，线材的挤出稳定性越差；
线径相对偏差：线径相对偏差是指某一次测量的绝对偏差占平均值的百分比，其中绝对偏差是指测定值与平均值之差；线径相对偏差值越大，线材的挤出稳定性越差。
表3 实施例1-6及对比例1的性能测试结果
Figure PCTCN2018092801-appb-000003
从表3中从实施例1-6和对比例1可以看出，当聚乳酸3D打印材料的结构满足如下关系式：0℃≤Tx-Ty≤60℃时，该聚乳酸3D打印材料在拉线挤出速度为45Kg/h，挤出线材线径为1.75cm时，线材线径极差≤0.12cm，线材线径相对偏差<5％，从而展现出良好的线材挤出稳定性；对比例1中，线材线径极差>0.12cm，线材线径相对偏差大于5％，线材挤出稳定性较差。

Claims (7)

  1. 一种聚乳酸3D打印材料，其特征在于，按重量份数计，包括如下组分:
    (a)聚乳酸  98.0～100份；
    (b)加工助剂  0～2.0份；
    其中，基于整个聚乳酸的总重量，所述聚乳酸的右旋体的重量含量为0.3％～5％；
    该聚乳酸3D打印材料的结构满足如下关系式：
    0℃≤Tx-Ty≤60℃,
    其中，Tx是聚乳酸3D打印材料的最大失重速率温度，Ty是聚乳酸3D打印材料的外推起始分解温度。
  2. 根据权利要求1所述的一种聚乳酸3D打印材料，其特征在于，所述聚乳酸3D打印材料的最大失重速率温度Tx和外推起始分解温度Ty的测试方法：采用NETZCH公司的TG209型热重分析仪，在氮气气氛下测定聚乳酸3D打印材料的热失重DTG曲线和TG曲线，DTG曲线的峰顶温度为最大失重速率温度Tx,TG曲线下降段的切线与基线的交点为外推起始分解温度Ty；选择升温速率为10℃/min。
  3. 根据权利要求1所述的一种聚乳酸3D打印材料，其特征在于，所述聚乳酸3D打印材料的结构满足如下关系式：
    5℃≤Tx-Ty≤50℃,
    优选的，所述聚乳酸3D打印材料的结构满足如下关系式：
    10℃≤Tx-Ty≤40℃,
    其中，Tx是聚乳酸3D打印材料的最大失重速率温度，Ty是聚乳酸3D打印材料的外推起始分解温度。
  4. 根据权利要求1-3任一项所述的一种聚乳酸3D打印材料，其特征在于，基于整个聚乳酸的总重量，所述聚乳酸的右旋体的重量含量为0.5％～3％。
  5. 根据权利要求1-3任一项所述的一种聚乳酸3D打印材料，其特征在于，所述加工助剂选自硬酯酰胺、油酸酰胺、芥酸酰胺、硬脂酸锌、金属皂的高分子复合酯、乙撑双硬脂酰胺、聚乙烯蜡、硅酮类润滑剂中的一种或两种以上的混合物。
  6. 根据权利要求1-3任一项所述的一种聚乳酸3D打印材料，其特征在于，所述聚乳酸3D打印材料在拉线挤出速度为45Kg/h，挤出线材线径为1.75cm时，线材线径极差≤0.12cm，线材线径相对偏差<5％。
  7. 一种聚乳酸3D打印线材，由权利要求1-6任一项所述的聚乳酸3D打印材料制备得到。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111747681A (zh) * 2020-07-08 2020-10-09 深圳升华三维科技有限公司 3d打印线材及其制备方法、3d打印产品的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109021515B (zh) * 2018-06-15 2020-03-17 金发科技股份有限公司 一种聚乳酸3d打印材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030148688A1 (en) * 1995-09-29 2003-08-07 Mamiko Matsunaga Biodegradable filament nonwoven fabric and method of producing the same
CN104987680A (zh) * 2015-03-18 2015-10-21 中广核三角洲（江苏）塑化有限公司 用于3d打印的高强度高耐热聚乳酸材料
CN106751613A (zh) * 2016-12-15 2017-05-31 江西师范大学 一种高韧性聚乳酸及其制备方法
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
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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104530666A (zh) * 2014-12-08 2015-04-22 安徽聚美生物科技有限公司 耐高温聚乳酸降解材料、耐高温聚乳酸注塑餐具及其制备方法
CN106893276A (zh) * 2015-12-18 2017-06-27 四川鑫达企业集团有限公司 一种高柔韧性和耐热性聚乳酸改性材料及其制备方法
CN106995596A (zh) * 2017-03-31 2017-08-01 华南理工大学 一种3d打印用的高结晶性pla材料及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030148688A1 (en) * 1995-09-29 2003-08-07 Mamiko Matsunaga Biodegradable filament nonwoven fabric and method of producing the same
CN104987680A (zh) * 2015-03-18 2015-10-21 中广核三角洲（江苏）塑化有限公司 用于3d打印的高强度高耐热聚乳酸材料
CN106751613A (zh) * 2016-12-15 2017-05-31 江西师范大学 一种高韧性聚乳酸及其制备方法
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
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111747681A (zh) * 2020-07-08 2020-10-09 深圳升华三维科技有限公司 3d打印线材及其制备方法、3d打印产品的制备方法

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