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CN111471261A - 一种生物基紫外光固化3d打印树脂及其制备方法 - Google Patents

一种生物基紫外光固化3d打印树脂及其制备方法 Download PDF

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CN111471261A
CN111471261A CN202010346877.1A CN202010346877A CN111471261A CN 111471261 A CN111471261 A CN 111471261A CN 202010346877 A CN202010346877 A CN 202010346877A CN 111471261 A CN111471261 A CN 111471261A
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洪英盛
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Shenzhen Intelligent Technology Co ltd
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Priority to PCT/CN2020/110123 priority patent/WO2021217962A1/zh
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Abstract

本发明公开了一种生物基紫外光固化3D打印树脂及其制备方法，重量百分比的组分组成包括生物可降解淀粉树脂聚合物19～78％、自由基引发剂1～9％、助剂0.2～4％、活性稀释剂13～62％、羟乙基淀粉2‑8％，将上述组分按比例混合，在50℃的水温下，用超声波清洗机超声10～20分钟后，再将其置于匀浆机搅拌均匀，得到生物基紫外光固化3D打印树脂。本发明采用可再生资源，减少环境污染及能源消耗，具有生物安全性。羟乙基淀粉具有链淀粉的葡萄糖环经羟乙基化形成的高分子复合物增加聚合速度，提高树脂成型的转化率，降低光引发剂及单体化学物质的比例。3D打印树脂性能优异，皮肤刺激值小。

Description

一种生物基紫外光固化3D打印树脂及其制备方法
技术领域
本发明涉及3D打印材料领域，尤其涉及的是一种生物基紫外光固化3D打印树脂及其制备方法。
背景技术
3D打印技术得到蓬勃发展，打印材料中的紫外光固化树脂大多数为不可回收材料，很容易造成环境污染，不具备生物安全性，且大多数具有性能较差、容易刺激皮肤等缺点。
因此，现有技术存在缺陷，需要改进。
发明内容
本发明所要解决的技术问题是：提供一种可生物降解、减少环境污染、性能好、皮肤刺激值小的生物基紫外光固化3D打印树脂及其制备方法。
本发明的技术方案如下：一种生物基紫外光固化3D打印树脂，重量百分比的组分组成包括生物可降解淀粉树脂聚合物19～78％、自由基引发剂1～9％、助剂0.2～4％、活性稀释剂13～62％。
采用上述技术方案，所述的生物基紫外光固化3D打印树脂中，所述生物可降解淀粉树脂聚合物由质量比为320g的生物可降解淀粉树脂、189g的聚乙二醇、0.2g的氢氧化钙、180g苯酐以及65g马来酸混合反应生成。
采用上述各个技术方案，所述的生物基紫外光固化3D打印树脂中，所述自由基引发剂为光引发剂1173、光引发剂184、光引发剂907、光引发剂TPO、光引发剂651、光引发剂819、光引发剂369、光引发剂DETX中的任意一种或几种组合。
采用上述各个技术方案，所述的生物基紫外光固化3D打印树脂中，所述助剂包括平流剂和消泡剂。
采用上述各个技术方案，所述的生物基紫外光固化3D打印树脂中，所述平流剂为聚二甲基硅氧烷、聚甲基苯基硅氧烷、有机硅改性聚硅氧烷中的任意一种。
采用上述各个技术方案，所述的生物基紫外光固化3D打印树脂中，所述平流剂为BYK-UV333、MOK-2120、B-0520中的任意一种或几种组合。
采用上述各个技术方案，所述的生物基紫外光固化3D打印树脂中，所述活性稀释剂为丙烯酸异冰片酯、丙烯酸四氢呋喃酯，丙烯酸异癸酯、十三烷基丙烯酸酯、聚乙二醇(400)二丙烯酸酯[PEG(400)DA]、环三羟甲基丙烷甲缩醛丙烯酸酯、2-苯氧基乙基丙烯酸酯、甲基丙烯酸环己酯、丙氧基化(2)新戊二醇二丙烯酸酯中的任意一种或几种组合。
一种制备上述生物基紫外光固化3D打印树脂的方法，制备方法为：
(1)、将生物可降解淀粉树脂、聚乙二醇以及氢氧化钙按照质量比混合，得到混合物；
(2)、将上述混合物在260℃下加热四小时，然后降温到120℃；
(3)、再加入苯酐和马来酸，并在260°温度下进行缩聚反应，得到生物可降解淀粉树脂聚合物；
(4)、将生物可降解淀粉树脂聚合物、自由基引发剂、助剂、活性稀释剂按照组分比例混合，在40°～50℃的水温下，用超声波清洗机超声10～20分钟后，再将其置于匀浆机搅拌均匀，得到生物基紫外光固化3D打印树脂；
采用上述各个技术方案，本发明具有如下有益效果：
1、采用可再生资源，减少环境污染及能源消耗，具有生物安全性。
2、通过添加羟乙基淀粉，通过其具有链淀粉的葡萄糖环经羟乙基化形成的高分子复合物增加聚合速度，提高树脂成型的转化率，降低光引发剂及单体化学物质的比例。
3、通过添加羟乙基淀粉、生物可降解淀粉树脂，达到3D打印成品可生物降解的效果。在使用完后进入自然环境中可依靠微生物、光和水等的作用自行分解，最终被分解为二氧化碳和氧气，几乎不对环境造成污染。
4、3D打印树脂性能优异，皮肤刺激值小。
具体实施方式
本发明提供一种生物基紫外光固化3D打印树脂及其制备方法，重量百分比的组分组成包括生物可降解淀粉树脂聚合物19～78％、自由基引发剂1～9％、助剂0.2～4％、活性稀释剂13～62％。
所述生物可降解淀粉树脂聚合物由质量比为320g的生物可降解淀粉树脂、189g的聚乙二醇、0.2g的氢氧化钙、180g苯酐以及65g马来酸混合反应生成。
所述自由基引发剂为光引发剂1173、光引发剂184、光引发剂907、光引发剂TPO、光引发剂651、光引发剂819、光引发剂369、光引发剂DETX中的任意一种或几种组合。
所述助剂包括平流剂和消泡剂。
所述平流剂为聚二甲基硅氧烷、聚甲基苯基硅氧烷、有机硅改性聚硅氧烷中的任意一种。
所述平流剂为BYK公司的BYK-UV333、德国默克公司的MOK-2120、中联邦化工公司的B-0520中的任意一种或几种组合。
所述活性稀释剂为丙烯酸异冰片酯、丙烯酸四氢呋喃酯，丙烯酸异癸酯、十三烷基丙烯酸酯、聚乙二醇(400)二丙烯酸酯[PEG(400)DA]、环三羟甲基丙烷甲缩醛丙烯酸酯、2-苯氧基乙基丙烯酸酯、甲基丙烯酸环己酯、丙氧基化(2)新戊二醇二丙烯酸酯中的任意一种或几种组合。
所述的羟乙基淀粉为湖北恒景瑞化工有限公司或上海康朗生物科技有限公司生产的现有产品。
制备上述生物基紫外光固化3D打印树脂的方法为：
(1)、将生物可降解淀粉树脂、聚乙二醇以及氢氧化钙按照质量比混合，得到混合物。采用320g的生物可降解淀粉树脂和189g的聚乙二醇进行酯交换反应，催化剂是0.2g的氢氧化钙。
(2)、将上述混合物在260℃下加热四小时，然后降温到120℃。
(3)、再加入180g苯酐和65g马来酸，并在260°温度下进行缩聚反应，直到酸值降低到初始值的10％以下，得到酸值为10.9mg KOH/g的生物可降解淀粉树脂聚合物。
(4)、将生物可降解淀粉树脂聚合物、自由基引发剂、助剂、活性稀释剂按照组分比例混合，在40°～50℃的水温下，用超声波清洗机超声10～20分钟后，再将其置于匀浆机搅拌均匀，得到生物基紫外光固化3D打印树脂。
根据上述技术方案，下面通过3个实施例与2个常规的3D打印树脂进行对比。
实施例1
生物可降解淀粉树脂聚合物，39g
活性稀释剂NPG(PO)2DA，47.5g
自由基光引发剂TPO，5g
BYK-333，2.5g
羟乙基淀粉，5g
BYK-UV3510，1g
按照以上比例调配好混合物，在50℃的水温下，用超声波清洗机超声20分钟，再将其置于匀浆机搅拌均匀，得到生物基紫外光固化3D打印树脂。
实施例2
生物可降解淀粉树脂聚合物，48.5g
活性稀释剂PEG(400)DA，39g
自由基光引发剂TPO，2g
自由基光引发剂819，2g
B-0520，2g
羟乙基淀粉，5.5g
MOK-2120，1g
按照以上比例调配混合物，在50℃的水温下，用超声波清洗机超声20分钟，再将其置于匀浆机搅拌均匀，得到生物基紫外光固化3D打印树脂。
实施例3
含生物可降解淀粉树脂(BSR)的聚合物，45.2g
活性稀释剂IBOA，42g
自由基光引发剂TPO，2g
自由基光引发剂369，2g
BYK-333，1.8g
羟乙基淀粉，6g
BYK-UV3510，1g
按照以上比例调配混合物，在40℃的水温下，用超声波清洗机超声10分钟，再将其置于匀浆机搅拌均匀，得到新一代环境及人体友好型植物油基紫外光固化3D打印树脂。
对比例1
普通聚酯型环氧丙烯酸树脂光固化3D打印树脂样品
对比例2
普通聚醚型聚氨酯丙烯酸酯光固化3D打印树脂
将上述3个实施例和2个常规对比例进行性能测试对比，得到表1的数据结果。
表1
Figure BDA0002470439690000051
Figure BDA0002470439690000061
通过上述对比，可以发现，3个实施例的打印树脂性能优于2个常规的打印树脂性能，3个实施例的打印树脂的皮肤刺激值也远小于2个常规的打印树脂。
采用上述各个技术方案，本发明具有如下有益效果：
1、采用可再生资源，减少环境污染及能源消耗，具有生物安全性。
2、通过添加羟乙基淀粉，通过其具有链淀粉的葡萄糖环经羟乙基化形成的高分子复合物增加聚合速度，提高树脂成型的转化率，降低光引发剂及单体化学物质的比例。
3、通过添加羟乙基淀粉、生物可降解淀粉树脂，达到3D打印成品可生物降解的效果。在使用完后进入自然环境中可依靠微生物、光和水等的作用自行分解，最终被分解为二氧化碳和氧气，几乎不对环境造成污染。
4、3D打印树脂性能优异，皮肤刺激值小。
以上仅为本发明的较佳实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (8)

1.一种生物基紫外光固化3D打印树脂，其特征在于，重量百分比的组分组成包括生物可降解淀粉树脂聚合物19～78％、自由基引发剂1～9％、助剂0.2～4％、活性稀释剂13～62％。
2.根据权利要求1所述的生物基紫外光固化3D打印树脂，其特征在于，所述生物可降解淀粉树脂聚合物由质量比为320g的生物可降解淀粉树脂、189g的聚乙二醇、0.2g的氢氧化钙、180g苯酐以及65g马来酸混合反应生成。
3.根据权利要求2所述的生物基紫外光固化3D打印树脂，其特征在于，所述自由基引发剂为光引发剂1173、光引发剂184、光引发剂907、光引发剂TPO、光引发剂651、光引发剂819、光引发剂369、光引发剂DETX中的任意一种或几种组合。
4.根据权利要求1所述的生物基紫外光固化3D打印树脂，其特征在于，所述助剂包括平流剂和消泡剂。
5.根据权利要求4所述的生物基紫外光固化3D打印树脂，其特征在于，所述平流剂为聚二甲基硅氧烷、聚甲基苯基硅氧烷、有机硅改性聚硅氧烷中的任意一种。
6.根据权利要求4所述的生物基紫外光固化3D打印树脂，其特征在于，所述平流剂为BYK-UV333、MOK-2120、B-0520中的任意一种或几种组合。
7.根据权利要求1所述的生物基紫外光固化3D打印树脂，其特征在于，所述活性稀释剂为丙烯酸异冰片酯、丙烯酸四氢呋喃酯，丙烯酸异癸酯、十三烷基丙烯酸酯、聚乙二醇(400)二丙烯酸酯[PEG(400)DA]、环三羟甲基丙烷甲缩醛丙烯酸酯、2-苯氧基乙基丙烯酸酯、甲基丙烯酸环己酯、丙氧基化(2)新戊二醇二丙烯酸酯中的任意一种或几种组合。
8.一种制备权1～7任一所述的生物基紫外光固化3D打印树脂，其特征在于，制备方法为：
(1)、将生物可降解淀粉树脂、聚乙二醇以及氢氧化钙按照质量比混合，得到混合物；
(2)、将上述混合物在260℃下加热四小时，然后降温到120℃；
(3)、再加入苯酐和马来酸，并在260°温度下进行缩聚反应，直到酸值降低到初始值的10％以下，得到酸值为10.9mg KOH/g的生物可降解淀粉树脂聚合物；
(4)、将生物可降解淀粉树脂聚合物、自由基引发剂、助剂、活性稀释剂按照组分比例混合，在40°～50℃的水温下，用超声波清洗机超声10～20分钟后，再将其置于匀浆机搅拌均匀，得到生物基紫外光固化3D打印树脂。
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