CN112341736B - 一种可用于3d打印的氟树脂组合物 - Google Patents

一种可用于3d打印的氟树脂组合物 Download PDF

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CN112341736B
CN112341736B CN202011130038.2A CN202011130038A CN112341736B CN 112341736 B CN112341736 B CN 112341736B CN 202011130038 A CN202011130038 A CN 202011130038A CN 112341736 B CN112341736 B CN 112341736B
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孙洪阳
周晓勇
陈振华
周承义
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Zhejiang Juhua Technology Center Co Ltd
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Abstract

本发明公开了一种可用于3D打印的氟树脂组合物，所述的氟树脂组合物包含氟树脂和含氟功能树脂。改性后的含氟功能材料作为增强体，通过机械共混的方式得到分散均匀的氟树脂组合物，所得制品具有较低的收缩性和良好的机械性能。该组合物可作为3D打印的原材料使用。

Description

一种可用于3D打印的氟树脂组合物
技术领域
本发明属于含氟聚合物的应用领域，具体涉及一种可用于3D打印的氟树脂组合物。
背景技术
3D打印技术即快速成型技术，材料通过逐层打印的方式来构造、加工物体的一种技术。3D打印因其精确、高效、快速的特点而越来越受到重视，然而可用于3D打印的高分子材料要求较高，目前已知的材料品种十分有限，如ABS、PC、PLA等。其中，聚偏氟乙烯(PVDF)因其良好的综合性能和加工性能而被视为可用于3D打印的含氟树脂材料。
然而PVDF是一种典型的结晶材料，其结晶度可以高达80％左右。由于结晶过程的存在，在加工成型过中，树脂从熔融态变为玻璃态时表现出较高的收缩性，此加工收缩性会影响3D打印过程，甚至导致3D打印成型失败。
专利US10259936公开了一种3D打印的含氟聚合物结构，采用添加PMMA或无机硬质填料来改善PVDF的收缩性能和翘曲问题，但是PMMA的加入在很大程度上牺牲了PVDF树脂的优异的化学耐受性，而常规硬质填料的表面性能与PVDF相差较大，界面不相容性会导致材料的综合性能，尤其是机械性能的下降，反而影响最终制品的使用。
因此，寻找一种既能改善树脂收缩性能，又能保证材料综合性能的方法十分必要。
发明内容
本发明的目的是提供一种可用于3D打印的氟树脂组合物，其特点在于选用含氟聚合物作为主体树脂，改性后的含氟功能材料作为增强体，通过机械共混的方式得到分散均匀的氟树脂组合物，所得制品具有较低的收缩性和良好的机械性能。该组合物可作为3D打印的原材料使用。
为了解决上述技术问题，本发明采用如下技术方案：
一种可用于3D打印的氟树脂组合物，其特征在于：所述的氟树脂组合物包含氟树脂和含氟功能树脂。
进一步，氟树脂为聚偏氟乙烯均聚物或偏氟乙烯单体和其他单体的共聚物。其他共聚单体包括氟化烯烃、氟化乙烯基醚、烯烃、乙烯基醚等，非限制性地包括三氟乙烯、氟乙烯、三氟氯乙烯、六氟丙烯、全氟丁基乙烯、全氟丙基乙烯基醚、丙烯、乙基乙烯基醚等。
进一步，氟树脂为粉末或粒料。
进一步，含氟功能树脂为至少包含乙烯和四氟乙烯结构单元的共聚物，乙烯单体和四氟乙烯单体的重量比为60/40-40/60。
进一步，含氟功能树脂为粉末材料。
进一步，含氟功能树脂为交联改性的乙烯-四氟乙烯共聚物。
进一步，交联改性方法为辐照加工或高温加工。辐照加工所采用的辐照源包括电子束、X射线、γ射线、微波、紫外线等。
进一步，高温加工为乙烯-四氟乙烯共聚物在150℃-250℃的空气环境中静置处理24小时-720小时，优选200-230℃，120小时-240小时。
乙烯-四氟乙烯共聚物在高温环境下，乙烯单元会发生断链反应生成乙烯自由基，乙烯自由基能够在分子链间或与氧气发生反应生成交联结构，从而使得原本长链结构的乙烯-四氟乙烯共聚物变成含有交联结构的改性乙烯-四氟乙烯共聚物。
进一步，氟树脂和含氟功能树脂的质量比为1:0.01-1。
进一步，氟树脂和含氟功能树脂组合物采用机械混合或乳液共凝聚的形式得到。
由于采用上述技术方案，本发明具有以下有益效果：
1.交联改性可以改变乙烯-四氟乙烯共聚物的分子链结构，使其成为有效的增强体。
2.交联改性乙烯-四氟乙烯共聚物与聚偏氟乙烯之间具有良好的界面相容性，能够解决普通硬质填料的界面问题。
附图说明
图1是实施例2中PVDF树脂和XETFE组合物注塑件的截面形貌图，截面较为均匀，无明显的相分离；
图2是对比例1中纯PVDF树脂注塑件的截面形貌图，截面均匀；
图3是对比例2中PVDF树脂同无机填料二氧化硅组合物注塑件的截面形貌图，出现明显的无机填料和PVDF树脂的相分离现象。
具体实施方式
以下结合具体实施方式对本发明的内容进行详细说明。
材料：
1.聚偏氟乙烯均聚物粉末，熔点165℃
2.乙烯-四氟乙烯共聚物粉末(含3重量％的全氟丙基乙烯基醚)，熔点250℃
测试方法：
1.采用模压成型技术来制备拉伸测试样条；拉伸性能测试按照GB/T 1040.1-2006进行。
2.采用注塑机来制备收缩性测试样条；收缩性测试按照GB/T 15585-1995进行。
3.采用场发射扫描电镜观察填料同基体树脂的相容性，方法如下：将注塑件浸入液氮中淬断，断面喷金处理后测扫描电镜；扫描电镜测试按照JY/T 010-1996进行。
4.采用熔融指数仪对ETFE粉末和交联改性的ETFE粉末进行熔融指数测试，测试条件为：温度297℃，砝码5kg。
实施例1
(1)将乙烯-四氟乙烯共聚物(ETFE)粉末放置在180℃的鼓风烘箱中，放置时间为72小时，得到交联改性的ETFE粉末(XETFE)，对ETFE和XETFE进行熔指测试，测试结果见表1；
(2)将步骤(1)得到的XETFE与偏氟乙烯均聚物(PVDF)粉末进行物理混合，使其混合均匀后备用，其中PVDF与XETFE的质量比为1:0.05；
(3)将步骤(2)得到的混合粉末通过模压机和注塑机制得相应的测试样品，并进行相关测试。测试结果见表2。
实施例2
(1)将乙烯-四氟乙烯共聚物(ETFE)粉末放置在220℃的鼓风烘箱中，放置时间为120小时，得到交联改性的ETFE粉末(XETFE)，对ETFE和XETFE进行熔指测试，测试结果见表1；
(2)将步骤(1)得到的XETFE与偏氟乙烯均聚物(PVDF)粉末进行物理混合，使其混合均匀后备用，其中PVDF与XETFE的质量比为1:0.2；
(3)将步骤(2)得到的混合粉末通过模压机和注塑机制得相应的测试样品，并进行相关测试。测试结果见表2。
实施例3
(1)将乙烯-四氟乙烯共聚物(ETFE)粉末放置在240℃的鼓风烘箱中，放置时间为360小时，得到交联改性的ETFE粉末(XETFE)，对ETFE和XETFE进行熔指测试，测试结果见表1；
(2)将步骤(1)得到的XETFE与偏氟乙烯均聚物(PVDF)粉末进行物理混合，使其混合均匀后备用，其中PVDF与XETFE的质量比为1:0.4；
(3)将步骤(2)得到的混合粉末通过模压机和注塑机制得相应的测试样品，并进行相关测试。测试结果见表2。
实施例4
(1)采用电子加速器对ETFE粉末进行辐照处理，辐照剂量为20MRad，得到交联改性的ETFE粉末(XETFE)，对ETFE和XETFE进行熔指测试，测试结果见表1；
(2)将步骤(1)得到的XETFE与偏氟乙烯均聚物(PVDF)粉末进行物理混合，使其混合均匀后备用，其中PVDF与XETFE的质量比为1:0.2；
(3)将步骤(2)得到的混合粉末通过模压机和注塑机制得相应的测试样品，并进行相关测试。测试结果见表2。
对比例1
将PVDF粉末通过模压机和注塑机制得相应的测试样品，并进行相关测试。测试结果见表2。
对比例2
(1)将碳粉与PVDF粉末进行物理混合，使其混合均匀后备用，其中PVDF与二氧化硅的质量比为1:0.2；
(2)将步骤(1)得到的混合粉末通过模压机和注塑机制得相应的测试样品，并进行相关测试。测试结果见表2。
表1.粉末测试结果
Figure BDA0002734834550000051
表2.样品测试结果
Figure BDA0002734834550000052
Figure BDA0002734834550000061
以上仅为本发明的具体实施例，但本发明的技术特征并不局限于此。任何以本发明为基础，为解决基本相同的技术问题，实现基本相同的技术效果，所作出地简单变化、等同替换或者修饰等，皆涵盖于本发明的保护范围之中。

Claims (5)

1.一种可用于3D打印的氟树脂组合物，其特征在于：所述的氟树脂组合物包含氟树脂和含氟功能树脂，所述氟树脂为聚偏氟乙烯均聚物或偏氟乙烯单体和其他单体的共聚物，所述含氟功能树脂为交联改性的乙烯-四氟乙烯共聚物，所述交联改性方法为辐照加工或高温加工，所述高温加工为乙烯-四氟乙烯共聚物在150℃-250℃的空气环境中静置处理24小时-720小时。
2.根据权利要求1所述一种可用于3D打印的氟树脂组合物，其特征在于：所述氟树脂为粉末或粒料。
3.根据权利要求1所述一种可用于3D打印的氟树脂组合物，其特征在于：所述含氟功能树脂为粉末材料。
4.根据权利要求1所述一种可用于3D打印的氟树脂组合物，其特征在于：所述氟树脂和含氟功能树脂的质量比为1:0.01-1。
5.根据权利要求1所述一种可用于3D打印的氟树脂组合物，其特征在于：所述氟树脂和所述含氟功能树脂组合物采用机械混合或乳液共凝聚的形式得到。
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