WO2018090801A1 - 一种聚乳酸3d打印线材及其制备方法 - Google Patents

一种聚乳酸3d打印线材及其制备方法 Download PDF

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Publication number
WO2018090801A1
WO2018090801A1 PCT/CN2017/107749 CN2017107749W WO2018090801A1 WO 2018090801 A1 WO2018090801 A1 WO 2018090801A1 CN 2017107749 W CN2017107749 W CN 2017107749W WO 2018090801 A1 WO2018090801 A1 WO 2018090801A1
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Prior art keywords
polylactic acid
temperature
rate
wire
wire rod
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PCT/CN2017/107749
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English (en)
French (fr)
Inventor
熊凯
袁志敏
蔡彤旻
黄险波
曾祥斌
焦健
苑仁旭
钟宇科
卢昌利
杨晖
麦开锦
董学腾
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ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Tianjin Kingfa Advanced Materials Co Ltd
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ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Tianjin Kingfa Advanced Materials Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the invention belongs to the technical field of polymer materials, and particularly relates to a polylactic acid 3D printing wire and a preparation method thereof.
  • Polylactic acid is a colorless and transparent liquid-lactic acid produced by modern biotechnology from corn starch-rich corn, and then undergoes a special polymerization process to produce a granular polymer material.
  • 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.
  • the invention further finds through research that when the structure of the polylactic acid 3D printing wire material satisfies the following relationship: 365 ° C ⁇ Tx ⁇ 385 ° C and 80 ° C ⁇ Tm - Tg ⁇ 115 ° C, the polylactic acid 3D printing wire is drawn at the drawing speed When the wire diameter is 40Kg/h and the extruded 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 printed wire having significantly improved extrusion stability.
  • Another object of the present invention is to provide a method for producing the above polylactic acid 3D printing wire.
  • a polylactic acid 3D printing wire in parts by weight, comprising the following components:
  • the structure of the polylactic acid 3D printed wire material satisfies the following relationship:
  • Tm is the melting point
  • Tg is the glass transition temperature
  • Tx is the maximum weight loss rate temperature
  • the test method of melting point Tm DSC test, the sample firstly heated from 30 ° C to 220 ° C at a heating rate of 10 ° C / min, and kept at 220 ° C for 3 min to eliminate the heat history, and then cooled at a rate of 10 ° C / min to At 30 ° C, and then at a rate of 10 ° C / min to 220 ° C, the second melting curve of the sample is obtained, the melting peak of the curve is selected as the melting point; the glass transition temperature Tg test method: DSC204 heat in Netzsch, Germany Performed on the analyzer and protected with nitrogen.
  • the sample with a mass of 5 ⁇ 1mg is first heated from 30°C to 160°C at a heating rate of 10°C/min, and kept at 160°C for 3min, then cooled to a temperature of 20°C/min. -110 ° C, and then ramped to 150 ° C at a rate of 10 ° C / min.
  • the glass transition temperature Tg of the sample is taken from the curve of the second temperature rise, and the intersection of the extension line at the bend and the baseline is taken as the value of the glass transition temperature Tg;
  • Test method for maximum weight loss rate temperature Tx Using NETZCH TG209 thermogravimetric analyzer, the thermal weight loss curve of the resin was measured under a nitrogen atmosphere. The peak top temperature of the DTG curve was the maximum weight loss rate temperature Tx; the heating rate was selected to be 10 °C. /min.
  • Tm-Tg refers to the difference between the melting point of the molecular structure and the glass transition temperature. It actually reflects the processing window width and extrusion stability of the polylactic acid 3D printed wire.
  • Tx refers to the maximum weight loss rate temperature, reflecting the weight loss.
  • the turning point temperature of the falling section of the curve has many factors affecting the difference between the Tx value and the Tm-Tg, such as the difference in the structure or ratio of the raw material monomers, the change in the molecular weight and molecular chain sequence structure, the influence of the addition of the lubricant component, and the preparation. Process factors (such as different process parameters) and other factors will affect the molecular structure of the final prepared polylactic acid 3D printed wire, which results in a significant difference between the Tx value and the Tm-Tg difference.
  • the invention finds out that when the structure of the polylactic acid 3D printing wire material satisfies the following relationship: 365 ° C ⁇ Tx ⁇ 385 ° C and 80 ° C ⁇ Tm - Tg ⁇ 115 ° C, the extrusion speed at the drawing line is 40 Kg / h, extrusion When the wire diameter is 1.75 cm, the wire diameter difference is ⁇ 0.12 cm, and the wire diameter relative deviation is ⁇ 5%, thereby exhibiting good extrusion stability.
  • the structure of the polylactic acid 3D printed wire material satisfies the following relationship:
  • the structure of the polylactic acid 3D printed wire material satisfies the following relationship:
  • Tm is the melting point
  • Tg is the glass transition temperature
  • Tx is the maximum weight loss rate temperature
  • the polylactic acid has a melt flow rate of 2 g/10 min to 8 g/10 min at 190 ° C under a load of 2.16 kg.
  • the lubricant 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 polylactic acid 3D printing wire has a wire drawing speed of 40 kg/h and an extruded wire diameter of 1.75 cm.
  • the wire diameter is very poor ⁇ 0.12cm, and the wire diameter relative deviation is ⁇ 5%.
  • the invention also provides a preparation method of the above polylactic acid 3D printing wire, comprising the following steps:
  • the polylactic acid and the lubricant are uniformly mixed in parts by weight, put into a twin-screw extruder, extruded at 160 ° C - 180 ° C, and granulated to obtain a composition;
  • composition obtained in the step (1) is drawn on a single-screw extruder, and the temperature of the water tank is controlled to be between 40 ° C and 60 ° C to obtain a polylactic acid 3D printed wire.
  • the water tank is divided into two water tanks, and the temperature of the first stage water tank is controlled to be 40° C. to 50° C., and the temperature of the second stage water tank is controlled to be 50° C. to 60° C.
  • the invention has the following beneficial effects:
  • the present inventors have found through research that when the structure of the polylactic acid 3D printing wire material satisfies the following relationship: 365 ° C ⁇ Tx ⁇ 385 ° C and 80 ° C ⁇ Tm - Tg ⁇ 115 ° C, the polylactic acid 3D printing wire is squeezed in the wire.
  • the exit speed is 40Kg/h and the wire diameter of the extruded wire is 1.75cm, the wire diameter difference is ⁇ 0.12cm, and the wire diameter relative deviation is ⁇ 5%, thereby exhibiting good wire extrusion stability;
  • the polylactic acid 3D printed wire prepared by controlling the extrusion process parameters has good extrusion stability.
  • the raw materials used in the present invention are as follows:
  • Polylactic acid purchased from Natureworks, USA, melt flow rate of 190 ° C, 2.16 kg load conditions of 5g/10min;
  • Lubricants erucamide, ethylene bis stearamide, and silicone masterbatch are all derived from commercially available products.
  • Example 1-6 Preparation of polylactic acid 3D printed wire
  • the PLA and the lubricant are uniformly mixed in the parts by weight shown in Table 1, and then put into a twin-screw extruder, extruded at 160 ° C - 180 ° C, and granulated to obtain a composition;
  • composition obtained in the step (1) is drawn on a single-screw extruder, and the temperature of the water tank is controlled to be between 40 ° C and 60 ° C to obtain a polylactic acid 3D printed wire material, wherein the extruded wire has a wire diameter of 1.75. Cm, the drawing speed of the drawing line is 40Kg/h, and the performance test results are shown in Table 1.
  • Embodiment 7 In step (2), the water tank is divided into two sections of water tanks, and the temperature of the first stage water tank is controlled to be 40 ° C - 50 ° C, and the control is performed. The temperature of the second stage is 50 ° C - 60 ° C, and the rest is the same as in Example 2.
  • Comparative Example 1 In the step (2), the temperature of the water tank was controlled to be between 65 and 70 ° C, and the rest was the same as in Example 2.
  • Comparative Example 2 PLA 95.0 parts, lubricant 5.0 parts, and the rest were the same as in Example 2.
  • Comparative Example 3 In the step (2), the temperature of the water tank was controlled to be between 65 and 70 ° C, and the rest was the same as in Example 1.
  • Melting point (Tm) test method DSC test: The sample is first heated from 30 ° C to 220 ° C at a heating rate of 10 ° C / min, and kept at 220 ° C for 3 min to eliminate the heat history, and then cooled at 10 ° C / min to At 30 ° C, the temperature was raised to 220 ° C at a rate of 10 ° C / min to obtain a second melting curve of the sample, and the melting peak of the curve was selected as the melting point.
  • melt flow rate ISO 1133, Plastics - Determination of mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics - Part 1: Standard method;
  • Test method for glass transition temperature (Tg) carried out on a DSC204 thermal analyzer from Netzsch, Germany, and protected with nitrogen.
  • the sample with a mass of 5 ⁇ 1 mg is first heated from 30 ° C to 160 ° C at a heating rate of 10 ° C / min. And kept at 160 ° C for 3 min, then cooled to -110 ° C at a rate of 20 ° C / min, and then increased to 150 ° C at a rate of 10 ° C / min.
  • the glass transition temperature (Tg) of the sample is taken from the curve of the second temperature rise, and the intersection of the extension line at the bend and the baseline is taken as the value of the glass transition temperature Tg;
  • Tx The maximum weight loss rate temperature (Tx) test method: using NETZCH TG209 type thermogravimetric analyzer, the thermal weight loss curve of the resin was measured under a nitrogen atmosphere, and the peak top temperature of the DTG curve was the maximum weight loss rate temperature (Tx); The rate is 10 ° C / min,;
  • 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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)

Abstract

本发明公开了一种聚乳酸3D打印线材及其制备方法，包括如下组分: (a)聚乳酸 99.0～100份； (b)润滑剂 0～1.0份；其中，该聚乳酸3D打印线材的结构满足如下关系式： 365℃≤Tx≤385℃且80℃≤Tm-Tg≤115℃, 其中，Tm为熔点，Tg为玻璃化转变温度，Tx为最大失重速率温度。本发明通过研究发现，当聚乳酸3D打印线材的结构满足如下关系式：365℃≤Tx≤385℃且80℃≤Tm-Tg≤115℃时，该聚乳酸3D打印线材在拉线挤出速度为40Kg/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打印线材及其制备方法 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打印线材及其制备方法。
背景技术
聚乳酸(PLA)是由饱含淀粉质的玉米经过现代生物技术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。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/m2，严重的限制了它的广泛应用。采用多组分共混改性的方法提高聚乳酸的韧性是目前的主要技术手段，但是各种相容性较差的组分的加入会影响聚乳酸挤出稳定性。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。
本发明通过研究进一步发现，当聚乳酸3D打印线材的结构满足如下关系式：365℃≤Tx≤385℃且80℃≤Tm-Tg≤115℃时，该聚乳酸3D打印线材在拉线挤出速度为40Kg/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打印线材，该聚乳酸3D打印线材具有明显改善的挤出稳定性。
本发明的另一目的在于提供上述聚乳酸3D打印线材的制备方法。
本发明是通过以下技术方案实现的：
一种聚乳酸3D打印线材，按重量份数计，包括如下组分:
(a)聚乳酸  99.0～100份；
(b)润滑剂  0～1.0份；
其中，该聚乳酸3D打印线材的结构满足如下关系式：
365℃≤Tx≤385℃且80℃≤Tm-Tg≤115℃,
其中，Tm为熔点，Tg为玻璃化转变温度，Tx为最大失重速率温度。
其中，熔点Tm的测试方法：DSC测试，样品先以10℃/min的升温速率从30℃升温到220℃，并在220℃保持3min以消除热历史，然后以10℃/min的速率降温至30℃，再以10℃/min的速率升温至220℃，得到样品的第二次熔融曲线，选取此曲线熔融峰值即为熔点；玻璃化转变温度Tg的测试方法：在德国Netzsch公司的DSC204热分析仪上进行，用氮气保护，质量为5±1mg的样品先以10℃/min的升温速率从30℃升温到160℃，并在160℃保持3min，然后以20℃/min的速率降温至－110℃，再以10℃/min的速率升温至150℃。样品的玻璃化转变温度Tg取自第二次升温的曲线，以拐弯处的外延线与基线交点作为玻璃化转变温度Tg的值；
最大失重速率温度Tx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曲线，DTG曲线的峰顶温度为最大失重速率温度Tx；选择升温速率为10℃/min。
Tm-Tg是指分子结构的熔点与玻璃化转变温度的差值，其实际反映的是聚乳酸3D打印线材的加工窗口宽窄及挤出稳定性，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，影响Tx值和Tm-Tg的差值的因素有很多，比如原料单体结构或比例的不同，分子量和分子链序列结构的变化，加入润滑剂组分的影响及制备工艺过程(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打印线材的分子结构存在较大区别，从而导致其Tx值和Tm-Tg的差值存在明显差异。
本发明通过研究发现，当聚乳酸3D打印线材的结构满足如下关系式：365℃≤Tx≤385℃且80℃≤Tm-Tg≤115℃时，在拉线挤出速度为40Kg/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打印线材的结构满足如下关系式：
370℃≤Tx≤380℃且95℃≤Tm-Tg≤110℃,
更优选的，所述聚乳酸3D打印线材的结构满足如下关系式：
372℃≤Tx≤378℃且98℃≤Tm-Tg≤107℃,
其中，Tm为熔点，Tg为玻璃化转变温度，Tx为最大失重速率温度。
所述聚乳酸的熔体流动速率在190℃、2.16kg载荷条件下为2g/10min-8g/10min。
所述润滑剂选自硬酯酰胺、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。
所述聚乳酸3D打印线材在拉线挤出速度为40Kg/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％。
本发明还提供了上述的一种聚乳酸3D打印线材的制备方法，包括如下步骤：
(1)将聚乳酸和润滑剂按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，得到组合物；
(2)将步骤(1)得到的组合物在单螺杆挤出机上进行拉线，控制水槽温度为40℃～60℃之间，即得聚乳酸3D打印线材。
优选的，步骤(2)中，水槽分为两段水槽，控制第一段水槽温度为40℃-50℃，控制第二段水槽温度为50℃-60℃。
本发明与现有技术相比，具有如下有益效果：
(1)本发明通过研究发现，当聚乳酸3D打印线材的结构满足如下关系式：365℃≤Tx≤385℃且80℃≤Tm-Tg≤115℃时，该聚乳酸3D打印线材在拉线挤出速度为40Kg/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；
(2)本发明在制备过程中，通过控制挤出的工艺参数，制备得到的聚乳酸3D打印线材具有良好的挤出稳定性。
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(PLA)：购自美国Natureworks公司，熔体流动速率在190℃、2.16kg载荷条件下为5g/10min；
润滑剂：芥酸酰胺、乙撑双硬脂酰胺、硅酮母粒均来源于市购产品。
实施例1-6：聚乳酸3D打印线材的制备
(1)将PLA和润滑剂按表1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，得到组合物；
(2)将步骤(1)得到的组合物在单螺杆挤出机上进行拉线，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40Kg/h，性能测试结果如表1所示。
实施例7：步骤(2)中水槽分为两段水槽，控制第一段水槽温度为40℃-50℃，控制 第二段水槽温度为50℃-60℃，其余同实施例2。
对比例1：步骤(2)中，控制水槽温度为65-70℃之间，其余同实施例2。
对比例2：PLA 95.0份，润滑剂5.0份，其余同实施例2。
对比例3：步骤(2)中，控制水槽温度为65-70℃之间，其余同实施例1。
性能测试方法：
熔点(Tm)的测试方法：DSC测试：样品先以10℃/min的升温速率从30℃升温到220℃，并在220℃保持3min以消除热历史，然后以10℃/min的速率降温至30℃，再以10℃/min的速率升温至220℃，得到样品的第二次熔融曲线，选取此曲线熔融峰值即为熔点。
熔体流动速率的测试方法：ISO 1133，塑料--热塑性塑料熔体质量流动速率(MFR)和熔体体积流动速率(MVR)的测定--第1部分：标准方法；
玻璃化转变温度(Tg)的测试方法：在德国Netzsch公司的DSC204热分析仪上进行，用氮气保护，质量为5±1mg的样品先以10℃/min的升温速率从30℃升温到160℃，并在160℃保持3min，然后以20℃/min的速率降温至－110℃，再以10℃/min的速率升温至150℃。样品的玻璃化转变温度(Tg)取自第二次升温的曲线，以拐弯处的外延线与基线交点作为玻璃化转变温度Tg的值；
最大失重速率温度(Tx)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曲线，DTG曲线的峰顶温度为最大失重速率温度(Tx)；选择升温速率为10℃/min，；
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1 实施例1-7及对比例1-2的性能测试结果
Figure PCTCN2017107749-appb-000001
从表1中从实施例1-7和对比例1-3可以看出，当聚乳酸3D打印线材的结构满足如下关系式：365℃≤Tx≤385℃且80℃≤Tm-Tg≤115℃时，该聚乳酸3D打印线材在拉线挤出速度为40Kg/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1-3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 (8)

  1. 一种聚乳酸3D打印线材，其特征在于，按重量份数计，包括如下组分:
    (a)聚乳酸  99.0～100份；
    (b)润滑剂  0～1.0份；
    其中，该聚乳酸3D打印线材的结构满足如下关系式：
    365℃≤Tx≤385℃且80℃≤Tm-Tg≤115℃,
    其中，Tm为熔点，Tg为玻璃化转变温度，Tx为最大失重速率温度。
  2. 根据权利要求1所述的一种聚乳酸3D打印线材，其特征在于，熔点Tm的测试方法：DSC测试，样品先以10℃/min的升温速率从30℃升温到220℃，并在220℃保持3min以消除热历史，然后以10℃/min的速率降温至30℃，再以10℃/min的速率升温至220℃，得到样品的第二次熔融曲线，选取此曲线熔融峰值即为熔点；
    玻璃化转变温度Tg的测试方法：在德国Netzsch公司的DSC204热分析仪上进行，用氮气保护，质量为5±1mg的样品先以10℃/min的升温速率从30℃升温到160℃，并在160℃保持3min，然后以20℃/min的速率降温至－110℃，再以10℃/min的速率升温至150℃；样品的玻璃化转变温度Tg取自第二次升温的曲线，以拐弯处的外延线与基线交点作为玻璃化转变温度Tg的值；
    最大失重速率温度Tx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曲线，DTG曲线的峰顶温度为最大失重速率温度Tx；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打印线材，其特征在于，所述聚乳酸3D打印线材的结构满足如下关系式：
    370℃≤Tx≤380℃且95℃≤Tm-Tg≤110℃,
    优选的，所述聚乳酸3D打印线材的结构满足如下关系式：
    372℃≤Tx≤378℃且98℃≤Tm-Tg≤107℃,
    其中，Tm为熔点，Tg为玻璃化转变温度，Tx为最大失重速率温度。
  4. 根据权利要求1-3任一项所述的一种聚乳酸3D打印线材，其特征在于，所述聚乳酸的熔体流动速率在190℃、2.16kg载荷条件下为2g/10min-8g/10min。
  5. 根据权利要求1-3任一项所述的一种聚乳酸3D打印线材，其特征在于，所述润滑剂选自硬酯酰胺、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打印线材，其特征在于，所述聚乳酸3D 打印线材在拉线挤出速度为40Kg/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. 根据权利要求1-6任一项所述的一种聚乳酸3D打印线材的制备方法，其特征在于，包括如下步骤：
    (1)将聚乳酸和润滑剂按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，得到组合物；
    (2)将步骤(1)得到的组合物在单螺杆挤出机上进行拉线，控制水槽温度为40℃～60℃之间，即得聚乳酸3D打印线材。
  8. 根据权利要求7所述的一种聚乳酸3D打印线材的制备方法，其特征在于，步骤(2)中，水槽分为两段水槽，控制第一段水槽温度为40℃-50℃，控制第二段水槽温度为50℃-60℃。
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