CN113929869B - 双组份3d打印用聚脲材料以及3d打印聚脲制品的方法 - Google Patents

双组份3d打印用聚脲材料以及3d打印聚脲制品的方法 Download PDF

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CN113929869B
CN113929869B CN202111432462.7A CN202111432462A CN113929869B CN 113929869 B CN113929869 B CN 113929869B CN 202111432462 A CN202111432462 A CN 202111432462A CN 113929869 B CN113929869 B CN 113929869B
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王占华
夏和生
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Abstract

本发明提供一种双组份3D打印用聚脲材料以及3D打印聚脲制品的方法，包括A、B组份；A组份为氨基封端的聚醚、聚酯、聚烯烃中的一种或几种混合物，或者为侧链含有氨基的聚醚、聚酯、聚烯烃中的一种或几种混合物；B组份由含异氰酸酯基团的化合物和含封端异氰酸酯的化合物组成，二者质量比例为3:1到1:4之间。所述的A、B组份经泵送制打印腔体混合，通过压力挤出打印，采用激光固化，循环重复此操作直至打印完成。本发明实现直写3D打印，可以打印出具有特殊复杂结构的聚脲制品，打印制品的Z方向上的强度可以达到XY平面的85％以上，可以获得机械性能不同的制品，包括弹性体，热固性树脂等，打印制品的透明度可调节，打印制品可以用于制备减震鞋底、儿童玩具、工艺品等。

Description

双组份3D打印用聚脲材料以及3D打印聚脲制品的方法
技术领域
本发明属于3D打印技术领域，具体涉及一种双组份3D打印用聚脲材料以及3D打印聚脲制品的方法。
背景技术
聚脲是由异氰酸酯组份与氨基化合物组份反应生成的一种弹性体物质。分为纯聚脲和半聚脲，他们的性能都是不一样的，聚脲的最基本的特性就是防腐、防水、耐磨等。聚脲防护涂料无溶剂、无污染，且在物料表面能快速成型，形成整体致密、连续无接缝的高强度、高弹性涂层，具有良好的耐磨抗冲击性能和耐海洋气候老化性能。现有一种聚脲防护涂料由高活性端氨基聚醚和多元胺扩链剂组成的R组份与多异氰酸酯预聚体组成的A组份反应制备而成，由于氨基与NC0基团间的反应速度非常快，因此成膜速度过快，导致涂层与基材之间的结合力及涂层之间的附着力较差，甚至出现不连续的涂层等缺陷，且给施工带来诸多困难。
聚脲最常用的加工方法为喷涂法，此方法适用于在各种基底上制备保护涂层。此外反应挤出成型法也可以用于聚脲的喷涂施工。目前关于聚脲3D打印技术的报道较少，一般为光固化3D技术。
近年来聚脲在军用器材减振、吸声阻尼领域也有着广泛的应用。利用3D打印技术构筑具有特殊结构的聚脲材料，可以提高其减振、吸声阻尼等性能，进一步提升其在军事领域的应用，具有重要意义。
申请号：2019107906039提供一种光敏树脂及一种3D打印聚脲的方法，所述光敏树脂包括含有脲键的且官能度大于等于2的丙烯酸酯齐聚物；所述含有脲键的且双键官能度大于等于2的丙烯酸酯齐聚物由官能度大于等于2的异氰酸酯基封端的化合物和含有氨基的丙烯酸酯或甲基丙烯酸酯化合物反应得到。本发明还提供了一种3D打印聚脲的方法。本发明提供的光敏树脂在光固化或3D打印形成聚合物之后，聚合物的分子结构、交联密度等网络结构特征可以经过特定的后处理进行改变，从而其热、力学性能也能通过后处理进行调整。该专利采用光固化技术进行3D打印，打印制品表面单体清除困难，环境污染严重，可打印单体种类有限，不适用于常用的双组份聚脲固化技术。
CN 113166355A提供双组份聚氨酯组合物的3D打印方法，包括如下步骤：-提供可泵送的第一组分A，所述第一组分A包含：至少一种多元醇，所述多元醇的OH官能度在1.5至4的范围内并且平均分子量(数均)Mn在250至15000g/mol的范围内，和优选至少一种二元醇，所述二元醇具有两个通过C2-至C9-碳链连接的羟基，和至少一种化合物T，所述化合物T具有至少一个巯基；-在连续混合器的混合区域中供入可泵送的第二组分B，其中所述第二组分B包含至少一种多异氰酸酯I；-其中两种组分A和B之一还包含至少一种用于羟基和异氰酸酯基团的反应的金属催化剂，所述金属催化剂可以形成含硫配合物，并且至少一种化合物T的所有巯基与至少一种金属催化剂的所有金属原子的摩尔比介于1:1和250:1之间。该方法打印的是聚氨酯的体系，需要有金属催化剂调节AB组份固化速率，金属催化剂对打印制品的性能影响较大，打印产品中含有硫元素，容易发生变黄降解。
CN101531861A提供一种双组份喷涂聚脲防水涂料，其制备方法及施工方法，其制备方法及施工方法，该防水涂料包括A组份和B组份，按重量计，A组份的原料体系包括多异氰酸酯40～60份、聚醚多元醇30～45份和5～15份羟基硅油；B组份的原料体系包括端氨基聚醚35～60份、胺类扩链剂20～45份以及5～20份氨基硅油。本发明防水涂料所形成的防水材料结合了聚脲弹性体和有机硅材料的优异性能，材料整体物理性能高、保色性优异、耐紫外线，可以应用于暴露在大气环境中的防水工程，特别适用于客运专线的路桥防水涂层。防水涂料的制备方法工艺简单、环保。采用本发明防水涂料的施工方法，可使涂料在基材表面上有效润湿和渗透基材，从而形成的防水涂层具有较好的外观。聚脲大多采用双组份喷涂工艺，使用与各种防水防腐涂层，制备的是涂层材料，不是具有特殊结构和功能的制件。
发明内容
本发明提供一种双组份3D打印用聚脲材料以及3D打印聚脲制品的方法，实现双组分聚脲直写3D打印：氨基与异氰酸酯反应速率极快，容易造成喷头堵塞，实现3D打印困难，拟通过引入封端异氰酸酯调节氨基与异氰酸酯固化速率及体系粘度，实现双组分聚脲直写3D打印。
双组份3D打印用聚脲材料，包括A、B组份；
A组份为氨基封端的聚醚、聚酯、聚烯烃中的一种或几种混合物，或者为侧链含有氨基的聚醚、聚酯、聚烯烃中的一种或几种混合物；
B组份由含异氰酸酯基团的化合物和含封端异氰酸酯的化合物组成，二者质量比例为3:1到1:4之间。
所述的A、B组份质量比为3:1到1:3之间。
所述的含异氰酸酯基团的化合物为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯三聚体、甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体中的一种或者几种的混合物。
所述的含封端异氰酸酯的化合物中采用的异氰酸酯封端剂为甲基乙基酮、肟、取代苯酚或者仲胺中的一种。
该双组份3D打印用聚脲材料的应用，作为3D打印材料。
3D打印聚脲制品的方法，采用所述的双组份3D打印用聚脲材料；包括以下过程：
所述的A、B组份经泵送制打印腔体混合，通过压力挤出打印，采用激光固化，循环重复此操作直至打印完成。
其中，打印机的挤出进料比为1:1到2:1之间。
打印机的打印速度为:200-800mm/min。
打印机的激光为广谱光源，激光固化时间：30秒到200秒。
本发明获得的聚脲制品具有较好的力学强度，拉伸强度可以达到10-60MPa，断裂伸长率为3％-2000％。
打印制品的Z方向上的强度可以达到XY平面的85％以上。
本发明的打印制品可以用于制备减震鞋底、儿童玩具、工艺品等。
本发明技术方案带来的有益效果：
1)A、B组份通过打印机混合，实现直写3D打印，可以打印出具有特殊复杂结构的聚脲制品；
2)在A、B组份混合过程中，氨基化合物首先与异氰酸酯化合物反应，实现预固化，增大体系的粘度，确保打印出的制件可以在基底上保持形状；
3)激光加热后固化，实现封端异氰酸酯解封端，继续与氨基发生固化反应，生成具有较好机械强度的制品，封端剂可以自由挥发去除；
4)引入封端异氰酸酯的有益效果是避免氨基与异氰酸酯固化太快，堵塞喷头；
5)由于聚脲分子链上的脲键可以形成氢键，同时在高温下可以发生交换反应，因此打印制品的Z方向上的强度可以达到XY平面的85％以上；
6)通过改变组份的化学成分，可以获得机械性能不同的制品，包括弹性体，热固性树脂等，打印制品的透明度也可以调节；
7)打印制品可以用于制备减震鞋底、儿童玩具、工艺品等。
附图说明
图1是实施例1打印制品的应力应变曲线；
图2是实施例1打印制品的光学照片；
图3是实施例2打印制品的应力应变曲线；
图4是实施例2打印制品的光学照片；
图5是实施例3中沿X、Y、Z方向分别打印的制品的拉伸强度；
图6是实施例3中沿X、Y、Z方向分别打印的制品的断裂伸长率。
具体实施方式
结合实施例说明本发明的具体技术方案。
实施例1
将10g二丙胺和16.63g六亚甲基二异氰酸酯混合，在室温搅拌24h,得到含封端异氰酸酯的化合物。
A组份采用分子量为4000的氨基封端的聚丙二醇，B组份为甲苯二异氰酸酯和上步骤获得的含封端异氰酸酯的化合物的混合物，二者质量比为1:2,A、B组份的质量比3:1，打印速度为300mm/min,激光固化时间60秒，进行3D打印。
如图1所示，通过此3D打印方法制备的聚脲断裂伸长率可以达到440％，具有很好的柔韧性。
如图2，通过此3D打印方法可以制备具有特殊复杂结构的透明聚脲制品。
实施例2
将10g二丙胺和17.8g甲苯二异氰酸酯，在室温搅拌24h,得到含封端异氰酸酯的化合物。
A组份采用分子量为230的氨基封端的聚丙二醇，B组份为二苯基甲烷二异氰酸酯和上步骤获得的含封端异氰酸酯的化合物的混合物，二者质量比为1:2,A、B组份的质量比1:1，打印速度为200mm/min,激光固化时间120秒，进行3D打印。
如图3，通过此3D打印方法制备的聚脲断裂强度可以达到57MPa，具有很好的机械性能。如图4为打印制品的光学照片，从此图可以得出，通过此3D打印方法可以制备具有特殊复杂结构的不透明白色聚脲制品。
实施例3
将10g甲基乙基酮肟和25.5g异氟尔酮二异氰酸酯，在室温搅拌24h,得到含封端异氰酸酯的化合物。
A组份采用分子量为400的氨基封端的聚乙二醇，B组份为异氟尔酮二异氰酸酯和上步骤获得的含封端异氰酸酯的化合物的混合物，二者质量比为1:1,A、B组份的质量比1:1，打印速度为500mm/min,激光固化时间60秒，进行3D打印。
图5为实施例3中沿X、Y、Z方向分别打印的制品的拉伸强度，从此图可以得出，沿着X、Y、Z三个方向打印的制品的拉伸强度基本相同，Z方向的强度可以达到X方向的90％，说明通过此3D打印技术可以获得机械性能各向同性的制件。
图6为实施例3中沿X、Y、Z方向分别打印的制品的断裂伸长率，从此图可以得出，沿着X、Y、Z三个方向打印的制品的断裂伸长率基本相同，说明通过此3D打印技术可以获得机械性能各向同性的制件。

Claims (5)

1.3D打印聚脲制品的方法，其特征在于，采用双组份3D打印用聚脲材料；
所述双组份3D打印用聚脲材料，包括A、B组份；
A组份为氨基封端的聚醚、聚酯、聚烯烃中的一种或几种混合物，或者为侧链含有氨基的聚醚、聚酯、聚烯烃中的一种或几种混合物；
B组份由含异氰酸酯基团的化合物和含封端异氰酸酯的化合物组成，二者质量比例为3:1 到1:4 之间；所述的含封端异氰酸酯的化合物中采用的异氰酸酯封端剂为甲基乙基酮、肟、取代苯酚或者仲胺中的一种；
方法包括以下过程：
所述的A、B组份经泵送至打印腔体混合，通过压力挤出打印，采用激光固化，循环重复此操作直至打印完成。
2.根据权利要求1所述的3D打印聚脲制品的方法，其特征在于，打印机的打印速度为:200-800 mm/min。
3.根据权利要求1所述的3D打印聚脲制品的方法，其特征在于，打印机的激光为广谱光源，激光固化时间：30秒到200秒。
4.根据权利要求1所述的3D打印聚脲制品的方法，其特征在于，所述的A、B组份质量比为3:1到1:3之间。
5.根据权利要求1所述的3D打印聚脲制品的方法，其特征在于，所述的含异氰酸酯基团的化合物为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯三聚体、甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体中的一种或者几种的混合物。
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