CN107936532A - 一种用于sls的硅橡胶粉体及其制备方法和应用 - Google Patents

一种用于sls的硅橡胶粉体及其制备方法和应用 Download PDF

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CN107936532A
CN107936532A CN201711268535.7A CN201711268535A CN107936532A CN 107936532 A CN107936532 A CN 107936532A CN 201711268535 A CN201711268535 A CN 201711268535A CN 107936532 A CN107936532 A CN 107936532A
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silicon rubber
powder
rubber powder
sls
small
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夏和生
甘鑫鹏
拉瓦叶纳·马里罗
王占华
孙劭杰
张春
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Sichuan University
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Sichuan University
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Abstract

本发明涉及3D打印材料技术领域，具体涉及一种用于SLS的硅橡胶粉体及其制备方法和应用，制备过程如下：将交联剂、氨基或羟基封端的聚二甲基硅氧烷、二异氰酸酯、异氰酸根封端的聚酯或聚醚、小分子二元醇溶解在有机溶剂中，加入二月桂酸二丁基锡催化剂，室温搅拌反应，固化24～96小时，得到硅橡胶；将硅橡胶、防老剂、热稳定剂通过挤出机混合均匀，造粒并通过机械研磨法或低温冷冻粉碎法制备成粉末，加入流动助剂混合均匀，筛分得到平均粒径为10～150um的粉体。本发明粉体的制备工艺简单，相对成本较低，制得硅橡胶粉体SLS打印制件有较高精度，力学性能良好，且具有较好的柔性，使SLS技术在打印人工皮肤、柔性电子器件、鞋底等方面得到应用。

Description

一种用于SLS的硅橡胶粉体及其制备方法和应用
技术领域
本发明涉及3D打印材料技术领域，具体涉及一种用于SLS的硅橡胶粉体及其制备方法和应用。
背景技术
3D打印技术是近些年兴起的一种新型加工成型技术，它以电脑三维设计模型为基础，将其切分成无数个剖面，在垂直方向上逐层打印堆积成三维实体。按加工原理和原材料形式的不同，目前的3D打印技术主要分为有熔融沉积技术、选择性激光烧结技术、分层实体制造技术和光固化成型技术。
选择性激光烧结技术(Selective laser sintering,SLS)是运用最为广泛的3D打印技术之一。其首先由美国C.R.Dechard等在专利US4863538提出，并于1989年成功研制出选择性激光烧结工艺设备。激光烧结为粉末材料为原料，通过计算机控制程序激光对粉体材料进行选择性逐层烧结，烧结完成后清除多余粉末即可得到3D打印制品。选择性激光烧结的材料来源广泛，金属、陶瓷和聚合物材料都可以用于此加工过程，其中聚合物材料因其优异的性能备受关注。由于目前材料制备技术的限制，目前应用于选择性激光烧结技术的聚合物材料主要是尼龙-12，其他聚合物材料，如聚碳酸酯、聚苯乙烯和聚醚醚酮等运用较少。这些材料价格相对传统加工工艺所需材料成本要高得多，同时这些材料通过选择性激光烧结工艺得到的制品通常有较大刚性，这严重研制了选择性激光烧结技术的应用领域。因此开发出一种适用于SLS的新的材料，尤其是柔性材料具有非常大的意义。
硅橡胶是一类以重复Si-O键为主链，硅原子上直接连接有机基团的的半无机、半有机结构高分子化合物，它兼具有无机和有机聚合物的特性，例如耐高低温、耐气候老化、电气绝缘、耐臭氧、疏水、气体透过性好且无毒、生物惰性等。被广泛应用于电子电气、建筑、汽车、纺织、医疗等领域。
发明内容
本发明的目的在于克服现有技术的不足，提供一种用于SLS的硅橡胶粉体及其制备方法和应用，本发明的硅橡胶粉体SLS打印制件有较高精度，力学性能良好，且具有较好的柔性，使SLS技术在打印人工皮肤、柔性电子器件、鞋底等方面得到应用，而且本发明制备工艺简单，成本相对较低。
本发明的目的是通过以下技术方案来实现的：
一种用于SLS的硅橡胶粉体，包括以下原料以物质的量份数计：
进一步地，所述交联剂为六亚甲基二异氰酸酯三聚体、甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体中的任一种。
进一步地，所述氨基或羟基封端的聚二甲基硅氧烷的分子量为900～30000。
进一步地，所述异氰酸根封端的聚酯或聚醚为聚己二酸乙二醇酯、聚己二酸乙二醇丙二醇酯、聚己二酸乙二醇丁二醇酯、聚ε-己内酯二醇中的任一种。
进一步地，所述小分子二元醇为2,2-二(4-羟基苯基)丙烷(双酚A)、4,4'-二羟基二苯砜(双酚S)、四氯双酚A、四溴双酚A、双酚F、联苯二酚、含Diels-Alder键二元醇中的任一种。
进一步地，所述有机溶剂为四氢呋喃、N,N-二甲基甲酰胺、1,4-二氧六环中的任一种。
进一步地，所述防老剂为N,N'-二苯基对苯二胺、9,9-二甲基吖啶、1-甲基-3,3'-二苯脲、N-苯基-N`-异丙基-对苯二胺、4,4一双(2,2-二甲基苄基)二苯胺中的任一种；所述热稳定剂为硬脂酸锌、硬脂酸钡、硬脂酸铅、钙盐、锌盐、铜盐、磷酸盐、硫醇甲基锡中的至少这一种；所述流动助剂为纳米氧化镁、纳米钛酸钡、滑石粉、高岭土、纳米钛白粉、纳米二氧化硅、纳米氧化铝中的至少一种。
一种制备如上述硅橡胶粉体的方法，包括以下步骤：
S1.将10～20份交联剂、20～40份氨基或羟基封端的聚二甲基硅氧烷、0～10份二异氰酸酯、0～15份异氰酸根封端的聚酯或聚醚、25～40份小分子二元醇溶解在有机溶剂中，加入1～2滴二月桂酸二丁基锡(DBTL)催化剂，室温搅拌反应4小时；反应结束后，将预聚物倒入聚四氟乙烯模具中，固化24～96小时，后从模具中取出得到氨基甲酸酯键的硅橡胶；
S2.将100份硅橡胶、0.1～0.5份防老剂、0.1～0.5份热稳定剂通过挤出机混合均匀，造粒并通过机械研磨法或低温冷冻粉碎法制备成粉末，加入0.1～0.5份流动助剂混合均匀，筛分得到平均粒径为10～150um的粉体。
进一步地，所述机械研磨法是将硅橡胶与助剂熔融混合后加入到机械研磨设备中，以100～600转/分钟的转速，粉碎后得到硅橡胶粉末材料；所述冷冻粉碎法是将硅橡胶与助剂熔融混合后加入到冷冻粉碎机中，在-196～-80℃的温度下，5000～20000转/分钟的转速冷冻粉碎后得到硅橡胶粉末材料。
一种如上述硅橡胶粉体的应用，将硅橡胶粉体平铺于选择性激光烧结设备的工作台上，设定温度60～65℃、单层厚度0.1mm、激光功率50～60w和扫描间距0.08～0.15mm，后进行3D打印。
优选地，在硅橡胶粉体的应用过程中，根据计算机CAD三维模型，激光在粉末材料表面特定区域进行选择性扫描、烧结，受激光照射的区域受热熔化，颗粒间发生粘合，一层烧结完毕后，工作缸下降设定的高度，再进行下一层的铺粉和烧结，并与前一层粘合，如此反复加工成型直至制件被完全打印出来，然后取出制件，即得到硅橡胶打印制件。
本发明的有益效果是：
1)合成的硅橡胶包含热可逆化学键，在高温下可断裂，降低温度又可重新生成，这一特性使得所制备的硅橡胶既具有重加工的性能，又能在无任何外加修复剂或催化剂的情况下实现自修复；
2)材料具有热加工性能，生物相容性较好；
3)制得的硅橡胶粉体可直接用于SLS成型，且打印制件具有良好的尺寸精度和力学性能，打印制件可应用于人工皮肤、柔性电子器件、鞋底等领域；
4)硅橡胶是一种柔性材料，极大拓宽了SLS在柔性打印方面的应用；
5)本发明说使用的原料易得，工艺简单易操作，产率高。
附图说明
图1为本发明试验例1得到的硅橡胶粉体的电镜扫描图；
图2为本发明试验例3得到的打印制件图；
具体实施方式
下面结合具体实施例和附图进一步详细描述本发明的技术方案，但本发明的保护范围不局限于以下所述。
实施例
一种制备如上述硅橡胶粉体的方法，包括以下步骤：
S1.将10～20份交联剂、20～40份氨基或羟基封端的聚二甲基硅氧烷、0～10份二异氰酸酯、0～15份异氰酸根封端的聚酯或聚醚、25～40份小分子二元醇溶解在有机溶剂中，加入1～2滴二月桂酸二丁基锡(DBTL)催化剂，室温搅拌反应4小时；反应结束后，将预聚物倒入聚四氟乙烯模具中，固化24～96小时，后从模具中取出得到氨基甲酸酯键的硅橡胶；
S2.将100份硅橡胶、0.1～0.5份防老剂、0.1～0.5份热稳定剂通过挤出机混合均匀，造粒并通过机械研磨法或低温冷冻粉碎法制备成粉末，加入0.1～0.5份流动助剂混合均匀，筛分得到平均粒径为10～150um的粉体。
具体地，所述机械研磨法是将硅橡胶与助剂熔融混合后加入到机械研磨设备中，以100～600转/分钟的转速，粉碎后得到硅橡胶粉末材料；所述冷冻粉碎法是将硅橡胶与助剂熔融混合后加入到冷冻粉碎机中，在-196～-80℃的温度下，5000～20000转/分钟的转速冷冻粉碎后得到硅橡胶粉末材料。
优选地，所述交联剂为六亚甲基二异氰酸酯三聚体、甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体中的任一种；所述氨基或羟基封端的聚二甲基硅氧烷的分子量为900～30000；所述异氰酸根封端的聚酯或聚醚为聚己二酸乙二醇酯、聚己二酸乙二醇丙二醇酯、聚己二酸乙二醇丁二醇酯、聚ε-己内酯二醇中的任一种；所述小分子二元醇为2,2-二(4-羟基苯基)丙烷(双酚A)、4,4'-二羟基二苯砜(双酚S)、四氯双酚A、四溴双酚A、双酚F、联苯二酚、含Diels-Alder键二元醇中的任一种；所述有机溶剂为四氢呋喃、N,N-二甲基甲酰胺、1,4-二氧六环中的任一种；所述防老剂为N,N'-二苯基对苯二胺、9,9-二甲基吖啶、1-甲基-3,3'-二苯脲、N-苯基-N`-异丙基-对苯二胺、4,4一双(2,2-二甲基苄基)二苯胺中的任一种；所述热稳定剂为硬脂酸锌、硬脂酸钡、硬脂酸铅、钙盐、锌盐、铜盐、磷酸盐、硫醇甲基锡中的至少这一种；所述流动助剂为纳米氧化镁、纳米钛酸钡、滑石粉、高岭土、纳米钛白粉、纳米二氧化硅、纳米氧化铝中的至少一种。
试验例1
称取9g氨丙基封端的聚二甲基硅氧烷DMS-A21(1.8mmol)、0.532g异佛尔酮二异氰酸酯(2.4mmol)、0.44g四氯双酚(1.2mmol)和0.2g六亚甲基二异氰酸酯三聚体(0.4mmol)溶解在20ml四氢呋喃中，室温搅拌反应3小时；再加入1滴二月桂酸二丁基锡(DBTDL)催化剂，室温继续反应1小时；反应结束后，将预聚物倒入聚四氟乙烯模具中，室温固化24小时，再放入60℃烘箱中继续固化24～48小时，后从模具中取出得到含双酚型动态氨基甲酸酯键的硅橡胶；将100份硅橡胶与0.2份N,N'-二苯基对苯二胺，0.2份硬脂酸锌混合均匀挤出造粒，加入到磨盘中以200转每分钟的速度研磨24小时，用150目的筛子筛出粉体，加入0.2份纳米二氧化硅混合均匀，得到中值粒径为50um的粉体，粉体的电镜扫描图如图1所示。
将粉末平铺于选择性激光烧结设备的工作台上，设定温度为60℃，单层厚度为0.1mm，激光功率为60w，扫描间距为0.15mm，进行3D打印得到打印制件。
试验例2
称取1.07g六亚甲基二异氰酸酯三聚体、1.52g含Diels-Alder键二元醇、3g异氰酸根封端的聚二甲基硅氧烷和0.62g异氰酸根封端的聚ε-己内酯于50mL圆底烧瓶中，加入25mL无水1,4-二氧六烷和两滴催化剂二月桂酸二丁基锡(DBTL)，在氮气保护下80℃搅拌反应24小时，搅拌过程中各组分逐渐溶解在溶剂中；待反应结束，70℃旋蒸除去大部分溶剂，得到可流动的粘稠预聚物；最后将预聚物倒入敞口的聚四氟乙烯模具，放置在80℃烘箱中让预聚物继续固化96小时，得到含Diels-Alder键的硅橡胶；
将100份硅橡胶与0.3份9,9-二甲基吖啶，0.2份硬脂酸钡混合均匀挤出造粒，加入到球磨机中以500转每分钟的速度研磨12小时，用150目的筛子筛出粉体，加入0.2份纳米氧化镁混合均匀，得到中值粒径为65um的粉体。
将粉末平铺于选择性激光烧结设备的工作台上，设定温度为60℃，单层厚度为0.1mm，激光功率为50w，扫描间距为0.08mm，进行3D打印得到打印制件。
试验例3
称取12g羟基封端的聚二甲基硅氧烷、0.642g异氰酸根封端的聚己二酸乙二醇酯、0.52g联苯二酚和0.3g甲苯二异氰酸酯三聚体溶解在30ml四氢呋喃中，加入1滴N,N-二甲基环己胺，室温搅拌反应4小时；再加入1滴二月桂酸二丁基锡(DBTDL)催化剂，室温继续反应1小时。反应结束后，将预聚物倒入聚四氟乙烯模具中，室温固化24小时，再放入60℃烘箱中继续固化24～48小时，后从模具中取出得到含双酚型动态氨基甲酸酯键的硅橡胶；
将100份硅橡胶与0.4份N-苯基-N`-异丙基-对苯二胺，0.2份铜盐磷酸盐混合均匀挤出造粒，加入到球磨机中以400转每分钟的速度研磨12小时，用100目的筛子筛出粉体，加入0.1份纳米氧化铝混合均匀，得到中值粒径为105um的粉体。
将粉末平铺于选择性激光烧结设备的工作台上，设定温度为65℃，单层厚度为0.1mm，激光功率为50w，扫描间距为0.10mm，进行3D打印得到打印制件，得到的打印制件如图2所示。
试验例4
称取2.41g二苯基甲烷二异氰酸酯三聚体、1.67g含Diels-Alder键二元醇、4g异氰酸根封端的聚二甲基硅氧烷和0.62g异氰酸根封端的聚己二酸乙二醇丙二醇酯于50mL圆底烧瓶中，加入25mL无水1,4-二氧六烷和两滴催化剂二月桂酸二丁基锡(DBTL)，在氮气保护下80℃搅拌反应24小时，搅拌过程中各组分逐渐溶解在溶剂中。待反应结束，70℃旋蒸除去大部分溶剂，得到可流动的粘稠预聚物；最后将预聚物倒入敞口的聚四氟乙烯模具，放置在80℃烘箱中让预聚物继续固化96小时，得到含Diels-Alder键的硅橡胶；
将100份硅橡胶与0.4份4,4一双(2.2-二甲基苄基)二苯胺，0.3份铜盐磷酸盐混合均匀挤出造粒，加入到冷冻粉碎机中，在-110℃下以6000转每分钟的速度粉碎，用150目的筛子筛出粉体，加入0.2份高岭土混合均匀，得到中值粒径为70um的粉体。
将粉末平铺于选择性激光烧结设备的工作台上，设定温度为65℃，单层厚度为0.1mm，激光功率为60w，扫描间距为0.15mm，进行3D打印得到打印制件。
将试验例1～4得到的打印制件进行力学性能检测，检测结果如表1所示。
表1试验例1～4得到的打印制件的力学性能表
项目 拉伸强度/MPa 断裂伸长率/％
实施例1 1.87 210.31
实施例2 1.92 215.72
实施例3 2.12 230.51
实施例4 2.03 225.46
以上所述仅是本发明的优选实施方式，应当理解本发明并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其他组合、修改和环境，并能够在本文所述构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围，则都应在本发明所附权利要求的保护范围内。

Claims (10)

1.一种用于SLS的硅橡胶粉体，其特征在于，包括以下原料以物质的量份数计：
2.根据权利要求1所述的一种用于SLS的硅橡胶粉体，其特征在于，所述交联剂为六亚甲基二异氰酸酯三聚体、甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体中的任一种。
3.根据权利要求1所述的一种用于SLS的硅橡胶粉体，其特征在于，所述氨基或羟基封端的聚二甲基硅氧烷的分子量为900～30000。
4.根据权利要求1所述的一种用于SLS的硅橡胶粉体，其特征在于，所述异氰酸根封端的聚酯或聚醚为聚己二酸乙二醇酯、聚己二酸乙二醇丙二醇酯、聚己二酸乙二醇丁二醇酯、聚ε-己内酯二醇中的任一种。
5.根据权利要求1所述的一种用于SLS的硅橡胶粉体，其特征在于，所述小分子二元醇为2,2-二(4-羟基苯基)丙烷(双酚A)、4,4'-二羟基二苯砜(双酚S)、四氯双酚A、四溴双酚A、双酚F、联苯二酚、含Diels-Alder键二元醇中的任一种。
6.根据权利要求1所述的一种用于SLS的硅橡胶粉体，其特征在于，所述有机溶剂为四氢呋喃、N,N-二甲基甲酰胺、1,4-二氧六环中的任一种。
7.根据权利要求1所述的一种用于SLS的硅橡胶粉体，其特征在于，所述防老剂为N,N'-二苯基对苯二胺、9,9-二甲基吖啶、1-甲基-3,3'-二苯脲、N-苯基-N`-异丙基-对苯二胺、4,4一双(2,2-二甲基苄基)二苯胺中的任一种；所述热稳定剂为硬脂酸锌、硬脂酸钡、硬脂酸铅、钙盐、锌盐、铜盐、磷酸盐、硫醇甲基锡中的至少这一种；所述流动助剂为纳米氧化镁、纳米钛酸钡、滑石粉、高岭土、纳米钛白粉、纳米二氧化硅、纳米氧化铝中的至少一种。
8.一种制备如权利要求1～7任意一项所述硅橡胶粉体的方法，其特征在于，包括以下步骤：
S1.将10～20份交联剂、20～40份氨基或羟基封端的聚二甲基硅氧烷、0～10份二异氰酸酯、0～15份异氰酸根封端的聚酯或聚醚、25～40份小分子二元醇溶解在有机溶剂中，加入1～2滴二月桂酸二丁基锡(DBTL)催化剂，室温搅拌反应4小时；反应结束后，将预聚物倒入聚四氟乙烯模具中，固化24～96小时，后从模具中取出得到氨基甲酸酯键的硅橡胶；
S2.将100份硅橡胶、0.1～0.5份防老剂、0.1～0.5份热稳定剂通过挤出机混合均匀，造粒并通过机械研磨法或低温冷冻粉碎法制备成粉末，加入0.1～0.5份流动助剂混合均匀，筛分得到平均粒径为10～150um的粉体。
9.根据权利要求8所述的硅橡胶粉体的制备方法，其特征在于，所述机械研磨法是将硅橡胶与助剂熔融混合后加入到机械研磨设备中，以100～600转/分钟的转速，粉碎后得到硅橡胶粉末材料；所述冷冻粉碎法是将硅橡胶与助剂熔融混合后加入到冷冻粉碎机中，在-196～-80℃的温度下，5000～20000转/分钟的转速冷冻粉碎后得到硅橡胶粉末材料。
10.一种如权利要求1～7任意一项所述硅橡胶粉体的应用，其特征在于，将硅橡胶粉体平铺于选择性激光烧结设备的工作台上，设定温度60～65℃、单层厚度0.1mm、激光功率50～60w和扫描间距0.08～0.15mm，后进行3D打印。
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