CN108623726B - 三维打印用腰果酚树脂及其制备方法 - Google Patents

三维打印用腰果酚树脂及其制备方法 Download PDF

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CN108623726B
CN108623726B CN201810460197.5A CN201810460197A CN108623726B CN 108623726 B CN108623726 B CN 108623726B CN 201810460197 A CN201810460197 A CN 201810460197A CN 108623726 B CN108623726 B CN 108623726B
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薛涵与
李心忠
林棋
方润
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Abstract

本发明涉及三维打印用腰果酚树脂及其制备方法。其制备方法如下：将腰果酚树脂或腰果酚衍生物与双烯类单体按质量比100:1~100:50混合，然后添加二者总质量1%的光引发剂并搅拌均匀，即得到三维打印用腰果酚树脂。该三维打印用腰果酚树脂可在紫外光辐照下，通过双烯类单体种类和用量的控制改变树脂基本物理性能和碳碳双键（C=C）的含量，即双烯类单体种类微调树脂使用性能，同时通过控制自由基的含量来实现腰果酚树脂的可控自由基交联聚合。该三维打印用腰果酚树脂可以适用于多种光固化三维打印技术，并可适用于制造脱胎漆器等漆器工艺品领域。

Description

三维打印用腰果酚树脂及其制备方法
技术领域
本发明属于三维打印树脂领域，具体涉及一种三维打印用腰果酚树脂及其制备方法。
背景技术
漆器工艺精湛、千文万华，特别是近代脱胎漆器是中国漆艺术瑰宝。然而，随着时代更迭，生漆价格高昂、漆器工艺复杂、价格高昂的短板凸显，市场需求大为减少，产业发展遇到瓶颈。
腰果酚从天然腰果壳油中经先进技术提炼而成，是一种可以代替或者部分代替漆酚的天然产物，具有价格低廉、低渗透性和自干性等特性。腰果酚分子（如图1所示）含有一个酚羟基，苯环上又有不饱和脂肪烃，同时具备酚和不饱和键的特性。目前的研究表明，腰果酚能够在紫外光辐照下实现交联固化。其机理是苯环上的不饱和脂肪烃中的碳碳双键（C=C）吸收紫外光而进行自由基交联。由于腰果酚不饱和脂肪烃中C=C含量较低，导致腰果酚在紫外光辐照下不易交联固化且交联不可控。
随着三维打印技术等新工艺的崛起，漆艺产业振兴重燃希望。然而目前腰果酚紫外光辐照聚合技术与漆酚一样，由于固化时间无法缩短至1-2min内，还难以应用于漆器的三维打印。因此，以振兴中国漆艺产业计，研发一种可直接三维制造的腰果酚树脂迫在眉睫。
发明内容
本发明的目的在于针对腰果酚树脂现有固化技术的不足，提供一种三维打印用腰果酚树脂及其制备方法。经本发明改性后的腰果酚树脂在紫外光辐照下容易交联固化且交联可控，紫外固化时间由原来的200s提升至10-100s。
为实现上述目的，本发明采用如下技术方案：
一种三维打印用腰果酚树脂的制备方法：将腰果酚树脂或腰果酚衍生物与双烯类单体按质量比100:1~100:50混合，然后添加二者总质量1%的光引发剂并搅拌均匀，即得到三维打印用腰果酚树脂。该三维打印用腰果酚树脂可通过光固化三维打印技术打印成型。
所述的腰果酚衍生物包括腰果酚缩醛、腰果酚冠醚中的一种。
所述的双烯类单体为1,3-戊二烯、1,4-己二烯中的一种。
所述的光引发剂为2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯基甲酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯中的一种。
所述的光固化三维打印技术为立体光固化成型技术（SLA）、数字光投影技术（DLP）、激光熔覆沉积技术（LCD）中的一种。
本发明将同时具有不饱和双键双烯类单体引入到腰果酚树脂中，并辅以紫外光引发剂加速腰果酚树脂的紫外光固化。该三维打印用腰果酚树脂通过双烯类单体用量的控制调控腰果酚树脂中碳碳双键（C=C）的含量，以此可控调节腰果酚树脂的紫外光自由基交联固化。同时，双烯类单体种类和用量又可调节腰果酚树脂中柔性链段的含量，进而调控腰果酚树脂的成型收缩率、弯曲性能等三维打印性能。这种三维打印用腰果酚树脂可适用于多种三维光固化成型技术。
一种如上所述的制备方法制得的三维打印用腰果酚树脂的可控固化方法：该三维打印用腰果酚树脂可在380nm紫外光辐照下，通过双烯类单体用量来改变树脂中碳碳双键（C=C）的含量，即控制自由基含量来实现腰果酚树脂的可控紫外光自由基交联聚合。研究结果表明，腰果酚树脂交联速率实现了提升与可控，即紫外固化时间由200s提升至30-100s，并且随着双烯类单体用量的变化而呈现递增趋势。
一种如上所述的三维打印用腰果酚树脂的使用性能调控方法：该三维打印用腰果酚树脂可通过调控双烯类单体用量来改变树脂中柔性链的含量，即调控腰果酚树脂的使用性能。研究结果表明，腰果酚树脂的成型收缩率随着双烯类单体用量的增大而略微增大，而弯曲性能则得到改善。
该三维打印用腰果酚树脂交联性能用凝胶含量测试，即交联度（详见实施例），无水乙醇为溶剂；成型收缩率测试以成形后树脂放置 24 小时，在温度为 23℃，相对湿度为50±5% 条件下测量出的相应尺寸之差；弯曲性能采用漆膜圆柱弯曲试验仪测试。
与现有技术相比，本发明涉及的三维打印用腰果酚树脂的优点在于：
该三维打印用腰果酚树脂具备腰果酚树脂的优异性能如热氧化稳定性、电绝缘性能、耐候性等；腰果酚树脂的紫外光快速固化，使其具备了在漆工艺自动化技术和增材制造技术领域的潜在应用能力；同时，通过双烯类单体种类和用量的调控不仅可以微调树脂使用性能和紫外光自由基交联聚合，还可以降低了腰果酚树脂的应用成本。三维打印用腰果酚树脂实现了复杂漆艺的快速成型。
附图说明
图1为本发明的腰果酚分子式；
图2为本发明的三维打印用腰果酚树脂光固化机理。
具体实施方式
下面结合实施例对本发明的技术方案作进一步的描叙，但不受限于这些实施例。
实施例 1
将腰果酚和1,3-戊二烯以质量比100:25混合，并添加二者总质量1%的光引发剂2-羟基-2-甲基-1-苯基丙酮，混合并搅拌均匀，即得到三维打印用腰果酚树脂。将三维打印用腰果酚树脂涂覆在马口铁上（厚度为100μm），在380nm紫外光（100μW/cm2）辐照下，腰果酚树脂可在20s内交联固化，交联度为87.5%，树脂膜弯曲性能达到7mm未出现裂痕。用3D打印机打印成样条，样条的成型收缩率为0.5%。
实施例 2
将腰果酚缩甲醛和1,4-己二烯以质量比100:50混合，并添加二者总质量1%的光引发剂2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮，混合并搅拌均匀，即得到三维打印用腰果酚树脂。将三维打印用腰果酚树脂涂覆在马口铁上（厚度为100μm），在380nm紫外光（100μW/cm2）辐照下，腰果酚树脂可在15s内交联固化，交联度为94.0%，树脂膜弯曲性能达到2mm未出现裂痕。用3D打印机打印成样条，样条的成型收缩率为0.2%。
实施例 3
将腰果酚冠醚和1,3-戊二烯以质量比100:25混合，并添加二者总质量1%的光引发剂2,4,6-三甲基苯甲酰基-二苯基氧化膦，混合并搅拌均匀，即得到三维打印用腰果酚树脂。将三维打印用腰果酚树脂涂覆在马口铁上（厚度为100μm），在380nm紫外光（100μW/cm2）辐照下，腰果酚树脂可在35s内交联固化，交联度为86.5%，树脂膜弯曲性能达到4mm未出现裂痕。用3D打印机打印成样条，样条的成型收缩率为0.5%。
实施例 4
将腰果酚冠醚和1,4-己二烯以质量比100:1混合，并添加二者总质量1%的光引发剂2,4,6-三甲基苯甲酰基苯基膦酸乙酯，混合并搅拌均匀，即得到三维打印用腰果酚树脂。将三维打印用腰果酚树脂涂覆在马口铁上（厚度为100μm），在380nm紫外光（100μW/cm2）辐照下，腰果酚树脂可在60s内交联固化，交联度为81.2%，树脂膜弯曲性能达到5mm未出现裂痕。用3D打印机打印成样条，样条的成型收缩率为0.5%。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (5)

1.一种三维打印用腰果酚树脂的制备方法，其特征在于：将腰果酚树脂或腰果酚衍生物与双烯类单体按质量比100:1~100:50混合，然后添加二者总质量1%的光引发剂，混合并搅拌均匀，即得到三维打印用腰果酚树脂；所述的双烯类单体为1,3-戊二烯、1,4-己二烯中的一种。
2.根据权利要求1所述的三维打印用腰果酚树脂的制备方法，其特征在于：所述的腰果酚衍生物包括腰果酚缩醛、腰果酚冠醚中的一种。
3.根据权利要求1所述的三维打印用腰果酚树脂的制备方法，其特征在于：所述的光引发剂包括2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯基甲酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯中的一种。
4.一种如权利要求1-3任一项所述的制备方法制得的三维打印用腰果酚树脂，其特征在于：紫外固化时间10-100s，成型收缩率低于0.5%，打印精度高。
5.一种如权利要求4所述的三维打印用腰果酚树脂的使用方法，其特征在于：该三维打印用腰果酚树脂在紫外光辐照下，通过双烯类单体种类和用量的控制改变树脂基本物理性能和碳碳双键的含量，即双烯类单体种类微调树脂使用性能，同时通过控制自由基的含量来实现腰果酚树脂的可控自由基交联聚合。
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