CN106521681A - 一种具有快速水溶性能的高强度3d打印支撑材料及其制备方法 - Google Patents

一种具有快速水溶性能的高强度3d打印支撑材料及其制备方法 Download PDF

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CN106521681A
CN106521681A CN201611029632.6A CN201611029632A CN106521681A CN 106521681 A CN106521681 A CN 106521681A CN 201611029632 A CN201611029632 A CN 201611029632A CN 106521681 A CN106521681 A CN 106521681A
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纪红兵
曾永斌
王晓红
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Zhenjiang Sanxin Material Co ltd
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Huizhou Research Institute of Sun Yat Sen University
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Abstract

本发明公开了一种具有快速水溶性能的高强度3D打印支撑材料及其制备方法。本发明将热塑性材料单体、丙烯酸类单体、乙酸乙烯酯进行溶液聚合得到含有羧酸基和酯基的预中和聚合物，再经中和催化后得到羧酸盐和醇羟基的中和聚合物，最后经去除溶剂、干燥和挤出拉丝，得到3D打印水溶性支撑线材。该材料具有优异的水溶性能，水溶速度是Stratasys 公司PC水溶式支撑材料SR‐100的10倍多；具有较高的强度，解决了PVA强度低不能起到支撑作用的问题；材料水溶后呈均一透明的溶液，解决了PVA水溶后黏糊浑浊，导致支撑材料处理困难的问题；材料无需使用增塑剂，具有无毒环保的特点。

Description

一种具有快速水溶性能的高强度3D打印支撑材料及其制备 方法
技术领域
本发明涉及3D打印材料的制备领域，具体地说，涉及一种具有快速水溶性能的高强度3D打印支撑材料及其制备方法。
背景技术
3D打印技术能够制造出复杂产品是传统制造无法比拟的巨大优势，但是，在3D打印复杂产品时需要打印大量支撑结构，这样，产品就面临着以下问题：①支撑结构去除困难，机械拆除不仅费时费力，还会损伤产品或留下印迹影响产品外观；②有机溶剂溶解支撑材料存在毒性和环保问题。因此，水溶性3D打印支撑材料是解决这些问题的最佳途径。目前，常用的水溶性支撑材料为PVA，但是该材料存在以下不足：①材料较软，强度低，不能很好的起到支撑作用，从而无法正常打印；②材料经水溶后会产生黏糊浑浊状态，导致边角和孔位等部位难以清理，从而支撑材料去除不理想。为解决PVA所存在的缺点，专利US6790403B1用丙烯酸树脂和增塑剂加工成线材用来打印支撑结构，并通过在一定温度的碱水溶液中溶解得到产品。该材料强度较高，可以实现支撑作用，同时溶解后呈均一透明溶液不产生黏糊现象，但是该材料仍然存在以下缺点：①材料的打印成型性能较差；②增塑剂的引入也不利于环保；③材料的水溶性能较差，溶解完全需要的时间较长。为进一步解决该类材料的打印成型和环保问题，专利WO2015175682A1不再添加增塑剂，而是在丙烯酸类单体中引入苯乙烯单体进行聚合，聚合完成后，用碱进行中和，最后得到3D打印水溶性支撑线材。该材料同样存在水溶性能较差的问题，严重影响了支撑材料去除的进度。
发明内容
本发明的目的是克服现有技术的不足，提供一种具有快速水溶性能的高强度3D打印支撑材料及其制备方法，本3D打印支撑材料具有水溶解速度快、溶解后呈均一透明无黏糊状溶液、强度高、支撑效果好、环保无毒等优点。
本发明实现上述目的技术方案是：
一种3D打印支撑材料，由以下方法制备而成：
1)溶液聚合：将热塑性材料单体、丙烯酸类单体、乙酸乙烯酯、引发剂、溶剂加入到反应容器中，热塑性材料单体、丙烯酸类单体、乙酸乙烯酯、引发剂、溶剂的质量份数之比为0.2～2:0.2～4:0.2～2:0.002～0.1:1，不断搅拌，在65℃～150℃恒温、冷凝回流的条件下反应5h～24h，得到预中和聚合物；
2)中和催化：将碱和溶剂混合后加入预中和聚合物中，碱、溶剂与单体总量的质量份数之比为0.01～0.1:0～2:1，不断搅拌，在常温常压下反应0.5h～24h，得到中和聚合物；
3)去除溶剂：将中和聚合物在温度为40℃～90℃和压力为-0.05MPa～-0.1MPa的条件下旋转蒸发0.2h～8h，得到去除溶剂的中和聚合物；
4)干燥：将中和聚合物在温度为60℃～150℃下干燥2h～48h，得到固态的中和聚合物；
5)挤出拉丝：将中和聚合物、抗氧剂、润滑剂混合均匀后加入到3D耗材挤出机中，加工温度为200℃～300℃，抗氧剂、润滑剂与中和聚合物的质量份数之比为0.0005～0.005:0.0005～0.005:1，经挤出、拉丝、风冷、绕卷，得到3D打印水溶性支撑线材。
作为优选的，步骤1)所述的热塑性材料单体为苯乙烯、丙烯腈、二乙烯基苯、丙烯酰胺中的至少一种。
作为优选的，步骤1)所述的丙烯酸类单体为丙烯酸、甲基丙烯酸、丙烯酸丁酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯中的至少一种。
作为优选的，步骤1)所述的引发剂为有机过氧化物类引发剂、无机过氧类引发剂和偶氮类引发剂中的至少一种。有机过氧化物类引发剂包括过氧化苯甲酰、过氧化月桂酰、二烷基过氧化物、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、过氧化甲乙酮、过氧化环己酮、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯；无机过氧类引发剂包括过硫酸钾、过硫酸钠、过硫酸铵等过硫酸盐，偶氮类引发剂包括偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯。
作为优选的，步骤1)所述的溶剂为乙醇、甲苯、二甲苯、四氢呋喃、乙酸乙酯、乙酸丁酯中的至少一种。
作为优选的，步骤2)所述的碱为氢氧化钾、氢氧化锂、氢氧化钠、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、氨水中的至少一种。
作为优选的，步骤2)所述的溶剂为水、乙醇、甲苯、二甲苯、四氢呋喃、乙酸乙酯、乙酸丁酯中的至少一种。
作为优选的，步骤5)所述的抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂、含硫类抗氧剂中的至少一种。
作为优选的，步骤5)所述的润滑剂为硅酮类润滑剂、蜡类润滑剂、酰胺类润滑剂、硬脂酸类润滑剂、含氟类润滑剂中的至少一种。
本发明将热塑性材料单体、丙烯酸类单体、乙酸乙烯酯进行溶液聚合得到含有羧酸基和酯基的预中和聚合物，再经中和催化后得到羧酸盐和醇羟基的中和聚合物，最后经去除溶剂、干燥和挤出拉丝，得到3D打印水溶性支撑线材。该材料具有以下优点：
①由于材料同时具有羧酸盐和醇羟基，具有优异的水溶性能，水溶速度是Stratasys公司PC水溶式支撑材料SR‐100的10倍多；
②材料具有较高的强度，解决了PVA强度低不能起到支撑作用的问题；
③材料水溶后呈均一透明的溶液，解决了PVA水溶后黏糊浑浊，导致支撑材料处理困难的问题；
④材料无需使用增塑剂，具有无毒环保的特点。
具体实施方式
下文中的重量份可以表示本领域常规的单位计量，如千克、克等，也可以表示的是各组分之间的比例，如质量或重量比等。
以下结合具体优选实施例对上述具有快速水溶性能的高强度3D打印支撑材料进行详细阐述。
实施例1：
步骤S11：将2Kg丙烯腈、1Kg丙烯酸、1Kg甲基丙烯酸、2Kg乙酸乙烯酯、20g偶氮二异丁腈、10Kg甲苯加入到反应容器中，不断搅拌，在150℃恒温、冷凝回流的条件下反应5h，得到预中和聚合物。
步骤S12：将60g氢氧化钠加入预中和聚合物中，不断搅拌，在常温常压下反应0.5h，得到中和聚合物。
步骤S13：将中和聚合物在温度为40℃和压力为-0.1MPa的条件下旋转蒸发0.2h，得到去除溶剂的中和聚合物。
步骤S14：将中和聚合物在温度为60℃下干燥48h，得到固态的中和聚合物。
步骤S15：将5Kg中和聚合物、1.25g抗氧剂1010、1.25g抗氧剂168、2.5g硬脂酸钙混合均匀后加入到3D耗材挤出机中，加工温度为200℃，经挤出、拉丝、风冷、绕卷，得到3D打印水溶性支撑线材。
实施例2：
步骤S21：将2Kg二乙烯基苯、2Kg甲基丙烯酸、2Kg丙烯酸乙酯、2Kg乙酸乙烯酯、100g过硫酸铵、1Kg乙酸乙酯加入到反应容器中，不断搅拌，在65℃恒温、冷凝回流的条件下反应24h，得到预中和聚合物。
步骤S22：将800g氢氧化锂溶解在16Kg乙酸乙酯后缓慢加入预中和聚合物中，不断搅拌，在常温常压下反应24h，得到中和聚合物。
步骤S23：将中和聚合物在温度为90℃和压力为-0.05MPa的条件下旋转蒸发8h，得到去除溶剂的中和聚合物。
步骤S24：将中和聚合物在温度为150℃下干燥2h，得到固态的中和聚合物。
步骤S25：将5Kg中和聚合物、12.5g抗氧剂1076、12.5g抗氧剂168、25g润滑剂PETS混合均匀后加入到3D耗材挤出机中，加工温度为300℃，经挤出、拉丝、风冷、绕卷，得到3D打印水溶性支撑线材。
实施例3：
步骤S31：将2Kg苯乙烯、2Kg甲基丙烯酸、2Kg丙烯酸丁酯、2Kg乙酸乙烯酯、48g过氧化苯甲酰、2Kg乙醇加入到反应容器中，不断搅拌，在80℃恒温、冷凝回流的条件下反应8h，得到预中和聚合物。
步骤S32：将240g氢氧化钾溶解在2Kg乙醇后缓慢加入预中和聚合物中，不断搅拌，在常温常压下反应1h，得到中和聚合物。
步骤S33：将中和聚合物在温度为50℃和压力为-0.08MPa的条件下旋转蒸发3h，得到去除溶剂的中和聚合物。
步骤S34：将中和聚合物在温度为120℃下干燥8h，得到固态的中和聚合物。
步骤S35：将5Kg中和聚合物、5g抗氧剂1010、5g抗氧剂168、10g润滑剂EBS混合均匀后加入到3D耗材挤出机中，加工温度为230℃，经挤出、拉丝、风冷、绕卷，得到3D打印水溶性支撑线材。
对比例1：
在实施例3中，将乙酸乙烯酯去除。
对比例2：
将实施例3中的材料替换成PVA材料。
相关性能测试：
将上述实施例1-3和对比例1-2提供的加工特点和产品性能如表1所示。
以上是对本发明实施例所提供的具有快速水溶性能的高强度3D打印支撑材料进行了详细介绍。
表1实施例和对比例加工特点和产品性能

Claims (9)

1.一种3D打印支撑材料，其特征在于由如下方法制备而成：
1）溶液聚合：将热塑性材料单体、丙烯酸类单体、乙酸乙烯酯、引发剂、溶剂加入到反应容器中，热塑性材料单体、丙烯酸类单体、乙酸乙烯酯、引发剂、溶剂的质量份数之比为0.2~2:0.2~4: 0.2~2:0.002~0.1: 1，不断搅拌，在65~150℃恒温、冷凝回流的条件下反应5h~24h，得到预中和聚合物；
2）中和催化：将碱和溶剂混合后加入预中和聚合物中，碱、溶剂与单体总量的质量份数之比为0.01~0.1:0~2:1，不断搅拌，在常温常压下反应0.5h~24h，得到中和聚合物；
3）去除溶剂：将中和聚合物在温度为40℃~90℃和压力为-0.05MPa~-0.1MPa的条件下旋转蒸发0.2h~8h，得到去除溶剂的中和聚合物；
4）干燥：将中和聚合物在温度为60℃~150℃下干燥2h~48h，得到固态的中和聚合物；
5）挤出拉丝：将中和聚合物、抗氧剂、润滑剂混合均匀后加入到3D耗材挤出机中，加工温度为200℃~300℃，抗氧剂、润滑剂与中和聚合物的质量份数之比为0.0005~0.005:0.0005~0.005:1，经挤出、拉丝、风冷、绕卷，得到3D打印水溶性支撑线材。
2.如权利要求1所述的3D打印支撑材料，其特征在于，步骤1）所述的热塑性材料单体为苯乙烯、丙烯腈、二乙烯基苯、丙烯酰胺中的至少一种。
3.如权利要求1所述的3D打印支撑材料，其特征在于，步骤1）所述的丙烯酸类单体为丙烯酸、甲基丙烯酸、丙烯酸丁酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯中的至少一种。
4.如权利要求1所述的3D打印支撑材料，其特征在于，步骤1）所述的引发剂为有机过氧化物类引发剂、无机过氧类引发剂和偶氮类引发剂中的至少一种。
5.如权利要求4所述的3D打印支撑材料，其特征在于，步骤1）所述的有机过氧化物类引发剂为过氧化苯甲酰、过氧化月桂酰、二烷基过氧化物、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、过氧化甲乙酮、过氧化环己酮、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯；无机过氧类引发剂为过硫酸钾、过硫酸钠或过硫酸铵；偶氮类引发剂为偶氮二异丁腈、偶氮二异庚腈或偶氮二异丁酸二甲酯。
6.如权利要求1所述的3D打印支撑材料，其特征在于，步骤1）所述的溶剂为乙醇、甲苯、二甲苯、四氢呋喃、乙酸乙酯、乙酸丁酯中的至少一种。
7.如权利要求1所述的3D打印支撑材料，其特征在于，步骤2）所述的碱为氢氧化钾、氢氧化锂、氢氧化钠、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、氨水中的至少一种。
8.如权利要求1所述的3D打印支撑材料，其特征在于，步骤2）所述的溶剂为水、乙醇、甲苯、二甲苯、四氢呋喃、乙酸乙酯、乙酸丁酯中的至少一种。
9.如权利要求1所述的3D打印支撑材料，其特征在于，步骤5）所述的抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂、含硫类抗氧剂中的至少一种；步骤5）所述的润滑剂为硅酮类润滑剂、蜡类润滑剂、酰胺类润滑剂、硬脂酸类润滑剂、含氟类润滑剂中的至少一种。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107868433A (zh) * 2017-11-30 2018-04-03 惠州市优恒科三维材料有限公司 一种水溶性3d打印支撑蜡及其制备方法
CN108503746A (zh) * 2018-04-28 2018-09-07 台州学院 一种水溶性3d打印支撑材料的制备与应用
CN110978501A (zh) * 2019-12-27 2020-04-10 珠海天威飞马打印耗材有限公司 一种常温三维打印方法和三维打印装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1635007A (zh) * 2004-12-01 2005-07-06 四川大学 疏水缔合水溶性共聚物及其制备方法
US20050189682A1 (en) * 2001-08-16 2005-09-01 Avraham Levy Reverse thermal gels as support for rapid prototyping
CN102408512A (zh) * 2011-10-19 2012-04-11 江苏三木集团有限公司 水溶性丙烯酸树脂的制备方法
CN103881289A (zh) * 2014-04-01 2014-06-25 上海材料研究所 一种可用于3d打印的改性聚甲醛支撑材料及其制备方法
CN105924882A (zh) * 2016-05-20 2016-09-07 黑龙江鑫达企业集团有限公司 一种可用于3d打印的支撑材料及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050189682A1 (en) * 2001-08-16 2005-09-01 Avraham Levy Reverse thermal gels as support for rapid prototyping
CN1635007A (zh) * 2004-12-01 2005-07-06 四川大学 疏水缔合水溶性共聚物及其制备方法
CN102408512A (zh) * 2011-10-19 2012-04-11 江苏三木集团有限公司 水溶性丙烯酸树脂的制备方法
CN103881289A (zh) * 2014-04-01 2014-06-25 上海材料研究所 一种可用于3d打印的改性聚甲醛支撑材料及其制备方法
CN105924882A (zh) * 2016-05-20 2016-09-07 黑龙江鑫达企业集团有限公司 一种可用于3d打印的支撑材料及其制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107868433A (zh) * 2017-11-30 2018-04-03 惠州市优恒科三维材料有限公司 一种水溶性3d打印支撑蜡及其制备方法
CN107868433B (zh) * 2017-11-30 2020-04-21 惠州市优恒科三维材料有限公司 一种水溶性3d打印支撑蜡及其制备方法
CN108503746A (zh) * 2018-04-28 2018-09-07 台州学院 一种水溶性3d打印支撑材料的制备与应用
CN110978501A (zh) * 2019-12-27 2020-04-10 珠海天威飞马打印耗材有限公司 一种常温三维打印方法和三维打印装置

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