CN109790647B - 用于3d打印机的基于丙烯的丝材 - Google Patents

用于3d打印机的基于丙烯的丝材 Download PDF

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CN109790647B
CN109790647B CN201780059541.3A CN201780059541A CN109790647B CN 109790647 B CN109790647 B CN 109790647B CN 201780059541 A CN201780059541 A CN 201780059541A CN 109790647 B CN109790647 B CN 109790647B
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ethylene copolymer
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heterophasic propylene
propylene ethylene
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R·德帕洛
C·卡瓦列里
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Basell Poliolefine Italia SRL
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Abstract

一种用于基于挤出的增材制造系统的可消耗丝材，其包含二甲苯可溶物含量为15wt％‑50wt％且熔体流动速率MFR L(熔体流动速率，根据ISO1133，条件L，即230℃和2.16kg负荷下)为0.5‑100g/10min的多相丙烯乙烯共聚物。

Description

用于3D打印机的基于丙烯的丝材
技术领域
本公开涉及用于基于挤出的3D打印机中的包含多相丙烯乙烯共聚物的丝材。
背景技术
基于挤出的3D打印机用于通过挤出可流动的造型材料以逐层方式从3D模型的数字表示构建3D模型。造型材料的丝材由挤出头的挤出尖端挤出，并在x-y平面中作为一系列道路沉积在底面上。挤出的造型材料熔到先前沉积的造型材料上，并在温度下降时固化。相对于底面，挤出头的位置沿z轴(垂直于x-y平面)增加，然后重复该过程以形成类似于数字表示的3D模型。根据表示3D模型的构建数据，挤出头相对于底面的移动在计算机控制下进行。通过将3D模型的数字表示初始分割成多个水平分割层来获得构建数据。然后，对于每个分割层，主计算机产生构建路径，用于造型材料的沉积道路以形成3D模型。
在打印过程中，丝材明显地起到了重要作用，改变丝材的材料，成品对象的最终机械和美学性能会改变。通常在本领域中使用聚乳酸(PLA)或丙烯腈、丁二烯、苯乙烯(ABS)聚合物或聚酰胺的丝材。
丝材最重要的特性之一是直径恒定(通常为1.75mm或3mm)，否则不可能微调打印对象中的材料量。这种性能不容易实现并且取决于聚合物的特性。
此外，一旦制备好，丝材必须是可打印的，即必须能够实现与板和层之间的良好附着。
已经提出基于丙烯的聚合物作为适合制造丝材的聚合物，然而从申请人进行的测试中，市场上可购得的基于丙烯的丝材在打印测试中效果较差。
因此，需要可在3D打印机中用作丝材的基于丙烯的聚合物。
发明内容
本申请人发现了一种用于基于挤出的增材制造系统的可消耗丝材，其包含二甲苯可溶物含量为15wt％-50wt％且熔体流动速率MFR L(熔体流动速率，根据ISO1133，条件L，即230℃和2.16kg负荷下)为0.5-100g/10min的多相丙烯乙烯共聚物。
附图说明
图1是在实施例的打印试验中使用的样品的前视图。测量以mm给出，样品一旦完全打印，厚度为5mm。
具体实施方式
本申请人发现了一种用于基于挤出的增材制造系统的可消耗丝材，其含有二甲苯可溶物含量为15wt％-50wt％、优选为20wt％-40wt％、更优选为22wt％-35wt％且熔体流动速率MFR L(熔体流动速率根据ISO1133，条件L，即230℃和2.16kg负荷下)为0.5-100g/10min、优选为2.0-50g/10min、更优选为5.0-20g/10min的多相丙烯乙烯共聚物。
在本发明中使用的表述“多相共聚物”表示弹性体丙烯乙烯共聚物(精细地)分散在基质中，如在丙烯均聚物或共聚物中。换句话说，弹性体丙烯乙烯共聚物在基质中形成夹杂物。因此，基质含非基质的一部分且(精细地)分散的夹杂物，所述夹杂物含有弹性体丙烯共聚物。根据本发明的术语“夹杂物”应优选地表示基质和夹杂物在多相体系内形成不同的相，所述夹杂物例如通过诸如电子显微镜或扫描力显微镜的高分辨率显微镜可见。
优选地，多相丙烯乙烯共聚物的乙烯含量为5wt％-30wt％、更优选为8wt％-25wt％、甚至更优选为10wt％-20wt％。
多相丙烯乙烯含量的基质可以是乙烯含量高达10wt％优选最多5wt％的丙烯均聚物或丙烯乙烯共聚物；优选地，基质是丙烯均聚物。
弹性体相是乙烯含量为12wt％-80wt％、优选30wt％-70wt％的丙烯乙烯共聚物。
25℃下可溶于二甲苯的级分的特性粘度优选为2.0-6.0dl/g、更优选为2.5-5.0dl/g、甚至更优选为3.1-4.5dl/g
术语共聚物是指仅由两种单体丙烯和乙烯形成聚合物。
术语二甲苯可溶物或二甲苯可溶物级分是指根据实施例部分中报告的程序测量的在25℃下可溶于二甲苯的级分。
本公开中使用的多相丙烯乙烯共聚物可以挤出成具有恒定直径的丝材，丝材的直径是本领域中使用的丝材的直径，例如1.75mm或3mm。也可以使用其它可能的直径。标称直径的变化为+/-0.05mm，优选+/-0.03mm。
当使用无定形聚合物材料，如丙烯腈-丁二烯-苯乙烯(ABS)树脂和聚碳酸酯树脂时，在固态时，它们的聚合物链很少或没有有序排列。这减少了在所得3D模型或支撑结构中的卷曲和塑性变形的影响。
结晶或半结晶聚合物表现出优异的机械性能，但是由于构建3D模型时的结晶度，在挤出道路被沉积以形成3D模型的层的一部分以及在道路被冷却时，它们都表现出不期望的收缩效果。收缩效应使得结晶或半结晶聚合物不能用于在基于挤出的增材制造工艺中构建3D对象。
申请人发现，本公开的多相丙烯乙烯共聚物可以有利地用于构建包含半结晶聚合物的3D模型，如二甲苯可溶物质的量所示。
本公开的丙烯乙烯共聚物可在市场上购得。共聚物的实施例可以是LyondellBasell出售的EP3080或EP3307。
本发明的丝材对象可另外含有本领域通常使用的添加剂，例如抗氧化剂、增滑剂、加工稳定剂、抗酸剂和成核剂。
丝材还可含有本领域已知的填料，例如滑石、碳酸钙、硅灰石、玻璃纤维、玻璃球和碳衍生等级。
此外，本发明的丝材还可包含木粉、金属粉末、大理石粉和通常用于具有特定美学外观或改进力学的3D对象的类似材料。
给出以下实施例以说明而非限制本发明。
实施例
丙烯聚合物材料的数据根据以下方法获得：
25℃下二甲苯可溶物级分
二甲苯可溶物级分根据ISO16152，2005测量，但具有以下偏差(括号间是ISO16152规定的)
溶液体积为250ml(200ml)
在25℃下30分钟的沉淀阶段期间，将溶液在最后10分钟内通过磁力搅拌器持续搅拌(30分钟，不进行任何搅拌)
最终干燥步骤在70℃(100℃)真空下进行
所述二甲苯可溶物级分的含量表示为初始2.5克的百分比，然后通过差值(与100互补)表示为，二甲苯不可溶％
乙烯(C2)含量
丙烯/乙烯共聚物的13C NMR
在装有低温探针的BrukerAV-600光谱仪上获得13C NMR光谱，在120℃下以傅里叶变换模式160.91MHz进行操作。
Sββ碳(根据“Monomer Sequence Distribution in Ethylene-Propylene RubberMeasured by 13C NMR.3.Use of Reaction Probability Mode(通过13C NMR测量的乙烯-丙烯橡胶中的单体序列分布.3.反应概率模式的应用)”CJ Carman，RA Harrington和CEWilkes，Macromolecules(大分子)，1977，10，536的命名法)的峰在29.9ppm处用作内参照。在120℃和8％wt/v浓度下将样品溶解在1，1，2，2-四氯乙烷d2中。用90°脉冲获得每个光谱，脉冲和CPD之间15秒的延迟可除去1H-13C耦合。使用9000Hz的谱窗将512个瞬态存储在32K数据点中。
谱的分配，三单元组分布和组成的评价是根据Kakugo(“Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymersprepared with δ-titanium trichloride-diethylalu minum chloride(碳-13NMR测定由δ-三氯化钛-二乙基氯化铝制备的乙烯-丙烯共聚物中的单体序列分布)”M.Kakugo，YNaito，K.Mizunuma和T.Miyatake，Macromolecules(大分子)，1982，15，1150)使用以下等式进行的：
PPP＝100Tββ/S PPE＝100Tβδ/S EPE＝100Tδδ/S
PEP＝100Sββ/S PEE＝100Sβδ/S EEE＝100(0.25Sγδ+0.5Sδδ)/S
S＝Tββ+Tβδ+Tδδ+Sββ+Sβδ+0.25Sγδ+0.5Sδδ
使用以下等式评价乙烯含量的摩尔百分比：
E％mol＝100*[PEP+PEE+EEE]使用以下等式评价乙烯含量的重量百分比：
Figure BDA0002008139810000051
其中P％mol是丙烯含量的摩尔百分比，而MWE和MWp分别是乙烯和丙烯的分子量。
竞聚率r1r2的乘积根据Carman(C.J.Carman，R.A.Harrington和C.E.Wilkes，Macromolecules(大分子)，1977；10，536)计算为：
Figure BDA0002008139810000052
丙烯序列的立构规整度由PPP mmTββ(28.90-29.65ppm)和整个Tββ(29.80-28.37ppm)的比率计算为mm含量。
熔体流动速率(MFR)
根据ISO1133(230℃，2.16Kg)测定聚合物的熔体流动速率MFR。
已使用了以下聚合物
PP1
具有MFR 6.5和在25℃下可溶于二甲苯的级分＜4％的丙烯均聚物
PP2
以商品名为PP REPRAP BLACK FIAMENT German RepRap PP Filament 600g出售的直径为1.75mm的商业丝材，无规丙烯乙烯共聚物(具有3wt％含量的乙烯，2dl/10min的MFR，6.2wt％的25℃下可溶于二甲苯的级分)。
PP3
以商品名为HIFAX EP3080出售的多相丙烯乙烯共聚物具有18wt％的乙烯含量，32.0wt％的二甲苯可溶物含量，7.5g/10min的MFR和3.5dl/g的二甲苯可溶物级分IV的特性粘度。
聚合物PP1和PP3已被挤出以形成直径为1.75mm的丝材。添加10wt％的滑石以挤出PP1。
打印试验
打印机是3D Rostock delta打印机。打印机条件如下：
Figure BDA0002008139810000071
待打印样品报告于图1中。对于每个丝材已经进行的5次打印机测试，当对象的一侧与平面分离时，打印已经停止，因此不再可能打印对象。结果报告于表1中
表1
材料 分离前的高度(Z)(mm)(平均值)
PP1* 0.8
PP2* 1.2
PP3 完整(5mm)
*对比
从表1清楚地看出，只有PP3，即根据本发明的材料，可用于完全打印样品。

Claims (10)

1.包含根据ISO16152，2005测量的二甲苯可溶物含量为15 wt%-50 wt%和根据ISO1133，条件L，即230℃和2.16 kg负荷的熔体流动速率为0.5-100 g/10 min的多相丙烯乙烯共聚物的可消耗丝材用作基于挤出的增材制造系统中的可消耗丝材的用途。
2.根据权利要求1所述的可消耗丝材的用途，其中在所述多相丙烯乙烯共聚物中，所述二甲苯可溶物含量为20 wt%-40 wt%。
3.根据权利要求1所述的可消耗丝材的用途，其中在所述多相丙烯乙烯共聚物中，所述根据ISO1133，条件L，即230℃和2.16 kg负荷的熔体流动速率为2.0-50.0 g/10 min。
4.根据权利要求1所述的可消耗丝材的用途，其中所述多相丙烯乙烯共聚物具有5wt%-30 wt%的乙烯含量。
5.根据权利要求1所述的可消耗丝材的用途，其中在所述多相丙烯乙烯共聚物中，基质是具有至多10 wt%含量的乙烯的丙烯均聚物或丙烯乙烯共聚物。
6.根据权利要求1所述的可消耗丝材的用途，其中在所述多相丙烯乙烯共聚物中，所述基质是丙烯均聚物。
7.根据权利要求1所述的可消耗丝材的用途，其中在所述多相丙烯乙烯共聚物中，25℃下可溶于二甲苯的级分的特性粘度为2.0-6.0 dl/g。
8.根据权利要求1所述的可消耗丝材的用途，其中在所述多相丙烯乙烯共聚物中，25℃下可溶于二甲苯的级分的特性粘度为2.5-5.0 dl/g。
9.一种根据权利要求1所述的可消耗丝材，其具有1.75 mm或3 mm+/-0.05 mm的直径。
10.根据权利要求9所述的可消耗丝材用于生产3D打印制品的用途。
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