CN112062917A - 一种光固化3d打印乙烯基星形聚磷酸酯复合光敏树脂及其制备方法和应用 - Google Patents
一种光固化3d打印乙烯基星形聚磷酸酯复合光敏树脂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于高分子材料技术领域,具体涉及一种光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂及其制备方法和应用。该材料包括以下重量百分含量的各组分:40%~70%的乙烯基星形聚磷酸酯高分子材料,5%~60%的交联剂,5%~25%的光引发剂,5%~40%的稀释剂,0%~25%的溶剂,0%~30%的填料。本发明所提供的光敏树脂在保持良好的生物相容性和可降解性的同时,能够采用光固化立体成形增材制造等技术进行加工,加工性能良好,具有重要的经济价值,应用范围广泛。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及一种光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂及其制备方法和应用。
背景技术
光固化立体增材制造技术(SLA)使用的原料为含有不饱和键的液态光敏树脂,也可在其中加入其它材料形成复合材料,采用计算机控制下的紫外激光束以计算机模型的各分层截面为路径逐点扫描,使被扫描区内的树脂薄层产生光聚合或光交联反应后固化,当一层固化完成后,在垂直方向移动工作台,使先前固化的树脂表面覆盖一层新的液态树脂,逐层扫描、固化,最终获得三维原型。SLA技术具有精度高、表面质量好、性能稳定、产品力学强度高等优点,其缺点是成型产品需要清洗除去杂质,可能造成产品变形,且光敏树脂价格较昂贵,一般不能降解。
发明内容
为解决现有技术的不足,本发明提供了一种光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂及其制备方法和应用。本发明所提供的光敏树脂在保持良好的生物相容性和可降解性的同时,能够采用光固化立体成形增材制造等技术进行加工,加工性能良好,具有重要的经济价值,应用范围广泛。
本发明所提供的技术方案如下:
一种光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂,包括以下重量百分含量的各组分:40%~70%的乙烯基星形聚磷酸酯高分子材料,5%~60%的交联剂,5%~25%的光引发剂,5%~40%的稀释剂,0%~25%的溶剂,0%~30%的填料,其中:
所述的乙烯基星形聚磷酸酯高分子材料选自申请号为201810488597.7中的如下结构通式:
其中,式I中的R1、R2各自独立选自氢原子、未取代的烷基、芳基,或者是带有至少一个羟基、至少一个氨基、至少一个羧基、至少一个烷氧基、至少一个芳基或至少一个芳氧基的烷基;R3、R4选自氢原子、烷基或者芳基;
式II中的R1、R2各自独立选自氢原子、未取代的烷基、芳基,或者是带有至少一个羟基、至少一个氨基、至少一个羧基、至少一个烷氧基、至少一个芳基或至少一个芳氧基的烷基;R3、R4选自氢原子、烷基或者芳基
式I或者式II中的n为1-100000的自然数;
所述的交联剂选自环己醇六烯丙基醚或环己醇六丙烯酸酯中的任意一种;
所述的填料选自乙烯基改性碳酸钙、羟基磷灰石中的任意一种。
上述技术方案所提供的光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂具有良好的光固化交联特性与高的光敏活性,适用于光固化立体成形3D打印,可用于制作个性化的体内植入物等医疗器械;经固化交联后形成的材料具有良好的生物相容性和可降解性,以及高力学强度、高韧性的特点。
聚磷酸酯的重复结构单元具有有机磷酸酯键的特点,从而赋予光敏树脂优良的生物相容性、可降解性,以及结构较易进行修饰和功能化性能。
由于乙烯基星形聚磷酸酯高分子材料具有优良的相容性与结构较易进行修饰和功能化等性能,因此交联剂的加入量可以高达60%。
具体的,所述的乙烯基星形聚磷酸酯高分子材料为:
其中n为1-100000的自然数;
或者为
其中n为1-100000的自然数;
或者为
其中n为1-100000的自然数;
或者为
其中n为1-100000的自然数。
优选的,乙烯基星形聚磷酸酯高分子材料占复合光敏树脂的重量百分比为45%~60%。
优选的,所述的交联剂占复合光敏树脂的重量百分比为20%~50%。
优选的,所述的填料占复合光敏树脂的重量百分比为0%~20%。
具体的,所述的光引发剂选自苯基-2,4,6-三甲基苯甲酰基膦酸锂、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任意一种或多种的混合;所述的光引发剂占复合光敏树脂的重量百分比为5%~25%。
具体的,所述的稀释剂为N-乙烯基吡咯烷酮或富马酸乙酯;所述的稀释剂占复合光敏树脂的重量百分比为5%~40%。
具体的,所述的溶剂为二氯甲烷、三氯甲烷、四氯化碳或二氯乙烷中的任意一种;所述的溶剂占复合光敏树脂的重量百分比为0%~25%。
在目前光固化3D打印机的紫外光(波长365nm±10nm,灯功率≥5w,光照强度400mw/cm2)照射下,在15秒时间内,本发明所提供的改性聚乳酸复合光敏树脂快速交联固化。较同类光固化3D打印机材料,固化时间进一步的缩短。
采用万能电子试验机按照国家标准GBT29284-2012、GBT16886进行测试,实验结果表明,经固化交联后形成的材料具有良好的生物相容性和可降解性,以及高力学强度、高韧性的特点。其中力学强度与韧性较采用含常见二乙烯基交联剂、未经乙烯基改性填料的光敏树脂提高60%以上。具体的性能数据和对比数据可以通过上述或其他现有的测试方法直接测试得到。
本发明还提供了上述光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂的制备方法,包括以下步骤:将各组分在常温条件下混合均匀,即得。
本发明还提供了上述光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂的应用,作为光固化立体成形3D打印材料。
具体实施方式
以下对本发明的原理和特征进行描述,所举实施例只用于解释本发明,并非用于限定本发明的范围。
实施例1
光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂(1000克)的配方如下:
实施例2
光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂(500克)的配方如下:
实施例3
光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂(200克)的配方如下:
实施例4
光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂(100克)的配方如下:
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂,其特征在于,包括以下重量百分含量的各组分:40%~70%的乙烯基星形聚磷酸酯高分子材料,5%~60%的交联剂,5%~25%的光引发剂,5%~40%的稀释剂,0%~25%的溶剂,0%~30%的填料,其中:
所述的乙烯基星形聚磷酸酯高分子材料具有如下结构通式:
式I或者式II中:R1、R2各自独立选自氢原子、未取代的烷基、芳基,或者是带有至少一个羟基、至少一个氨基、至少一个羧基、至少一个烷氧基、至少一个芳基或至少一个芳氧基的烷基;R3、R4各自选自氢原子、烷基或者芳基;
式I或者式II中的n为1-100000的自然数;
所述的交联剂选自环己醇六烯丙基醚或环己醇六丙烯酸酯中的任意一种;
所述的填料选自乙烯基改性碳酸钙、羟基磷灰石中的任意一种。
3.根据权利要求1所述的光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂,其特征在于:所述的光引发剂选自苯基-2,4,6-三甲基苯甲酰基膦酸锂、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任意一种或多种的混合。
4.根据权利要求1所述的光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂,其特征在于:所述的稀释剂为N-乙烯基吡咯烷酮或富马酸乙酯。
5.根据权利要求1所述的光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂,其特征在于:所述的溶剂为二氯甲烷、三氯甲烷、四氯化碳或二氯乙烷中的任意一种。
6.一种根据权利要求1至5任一所述的光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂的制备方法,其特征在于,包括以下步骤:将各组分在常温条件下混合均匀,即得。
7.一种根据权利要求1至5任一所述的光固化3D打印乙烯基星形聚磷酸酯复合光敏树脂的应用,其特征在于:作为光固化立体成形3D打印材料。
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