CN116284920A - 一种增强3d打印硅橡胶制品的制备试剂盒和制备方法 - Google Patents
一种增强3d打印硅橡胶制品的制备试剂盒和制备方法 Download PDFInfo
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- CN116284920A CN116284920A CN202310182596.0A CN202310182596A CN116284920A CN 116284920 A CN116284920 A CN 116284920A CN 202310182596 A CN202310182596 A CN 202310182596A CN 116284920 A CN116284920 A CN 116284920A
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- Prior art keywords
- silicone rubber
- diisocyanate
- printing
- reinforcing agent
- preparation
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Links
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明提供了一种增强3D打印硅橡胶制品的制备试剂盒和制备方法,通过使用特定的浸泡用增强液体系,对含有异氰酸酯基的聚硅氧烷聚氨酯材料3D打印制品进行浸泡处理,能够快速、简便地获得以高模量硅橡胶‑聚脲材料的3D打印制品,解决了高模量硅橡胶‑聚脲材料为固体无法进行室温3D直书写打印的问题,为机械性能优异的3D打印制品的制备提供了新策略。
Description
技术领域
本发明属于3D打印聚合物材料领域,具体涉及一种增强3D打印硅橡胶制品的制备试剂盒和制备方法。
背景技术
硅橡胶指分子链段中存在-Si-O-结构的线性聚硅氧烷交联形成的弹性体,具有良好弹性、热氧稳定性、生物惰性及透气性,在冲击防护、减震缓震、生物医用领域备受关注。此外,硅橡胶具有良好的加工性能,可通过浇铸、模压、旋涂等制备成型,满足不同应用场景。但上述加工方式仅限于制备几何结构简单的产品,随着各领域对复杂三维构件需求的增加,亟需引入新的加工技术。
增材制造(又称3D打印技术)因可实现计算机数字模拟三维结构的快速成型,可提高三维复杂构件的加工效率而受到关注。然而目前,受打印材料及打印设备的制约,仍然缺乏可打印的硅橡胶材料。以直书式3D打印(DIW)为例,打印材料必须满足具有剪切变稀和“自支撑性”的流变特性,即满足表观粘度随剪切速率增加而减小,且在未达到屈服剪切力时,材料可维持刚度保持形状。尽管大多数液体硅橡胶具备剪切变稀的流变特性,但并非都能满足“自支撑性”,因此,基于UV辅助的直书式3D打印技术应运而生。
UV辅助直书式3D打印技术借助紫外光固化技术,通过打印墨水的快速固化来维持打印骨架,实现了不具备“自支撑性”墨水(如光固化型液体硅橡胶)的3D打印。然而,通常满足打印条件的硅橡胶受分子量和分子链相互作用弱的限制,固化后力学性能较低,导致其应用受限。近年来,出现大量通过引入动态氢键提升硅橡胶力学性能的报道,然而氢键的引入同时引起硅橡胶室温下相态的转变,使其由液体转化为难溶固体,丧失打印性能。
综上所述,如何在增强硅橡胶机械性能的同时,使其兼具可打印性能,是本领域面临的技术难题。
发明内容
本发明的目的在于提供可通过浸泡工艺显著提升3D打印光固化材料机械性能的方法,以及用以浸泡的增强液体系;具体开发了一种通过再特定的增强液中浸泡从而在硅橡胶中形成多级次氢键,显著增强硅橡胶机械性能,实现3D打印硅橡胶-聚脲材料的方法。
为实现上述发明目的,本发明提供的技术方案如下:
本发明提供了增强剂溶液作为3D打印硅橡胶制品的增强液的用途,所述增强剂是官能团数量为2~4个的醇、胺或醇胺,所述增强剂溶液的溶剂为甲醇、异丙醇、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、丙酮、二氯甲烷、氯仿、乙酸乙酯、甲苯、N-甲基吡咯烷酮中的一种或几种;
所述3D打印硅橡胶制品的材料包括含有异氰酸酯基的聚硅氧烷聚氨酯,所述聚硅氧烷聚氨酯中异氰酸酯基的含量为0.3~5.21wt%,优选为0.32~2.7wt%。
进一步地,上述增强剂是乙二胺、1,6-己二胺、4,4'-亚甲基二(2-氯苯胺)、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、乙醇胺、二乙醇胺、三乙醇胺,优选为1,6-己二胺;
所述增强剂溶液的溶剂为异丙醇、水、四氢呋喃或N,N-二甲基乙酰胺;优选为异丙醇。
进一步地,上述增强剂溶液中增强剂浓度为0.1~0.3mmol/L,优选为0.3mmol/L。
本发明还提供了一种增强3D打印硅橡胶制品的制备试剂盒,由如下组分组成:
组分一:3D打印墨水;
组分二:增强剂溶液;
其中,3D打印墨水含有如下质量分数的原料:
光固化硅橡胶预聚体60~100%、光引发剂0.1~5%、活性稀释剂0~20%、功能填料0~40%;
所述光固化硅橡胶预聚体为含有乙烯基和异氰酸酯基的聚硅氧烷聚氨酯,乙烯基含量为0.35~2.93wt%,优选为1.03~1.74wt%,异氰酸酯基含量为0.3~5.21wt%,优选为0.32~2.7wt%;
增强剂溶液由如下原料组成:增强剂0.1~0.3mmol/L,余量为溶剂;
所述增强剂是官能团数量为2~4个的醇、胺或醇胺,所述溶剂为甲醇、异丙醇、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、丙酮、二氯甲烷、氯仿、乙酸乙酯、甲苯、N-甲基吡咯烷酮中的一种或几种。
进一步地,上述增强剂是乙二胺、1,6-己二胺、4,4'-亚甲基二(2-氯苯胺)、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、乙醇胺、二乙醇胺、三乙醇胺、甘油、三(2-氨基乙基)胺,优选为1,6-己二胺;
所述增强剂溶液的溶剂为异丙醇、水、四氢呋喃或N,N-二甲基乙酰胺;优选为异丙醇。
进一步地,上述增强剂浓度为0.3mmol/L。
进一步地,上述光固化硅橡胶预聚体的数均分子量为500~8000;
所述光引发剂为安息香双甲醚、2-羟基-2-甲基苯丙酮、2,4,6-三甲基苯甲酰基二苯基氧化膦,2-异丙基硫化杂蒽酮,二酰基膦氧化物、1-羟基-环己基-苯基甲酮中的一种或几种;
所述活性稀释剂是二异氰酸酯或丙烯酸酯类化合物,所述二异氰酸酯为:二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、间苯二甲基二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、氢化4,4-二苯甲烷二异氰酸酯中的一种或任意组合的混合物;
所述丙烯酸酯类化合物为:丙烯酸丁酯、丙烯酸十二醇酯、丙烯酸十六醇酯、丙烯酸异冰片酯、甲基丙烯酸羟乙酯、三丙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二季戊四醇丙烯酸酯中的一种或几种;
所述功能填料为白炭黑、炭黑、碳纳米管、石墨烯中的一种或几种。
进一步地,上述光固化硅橡胶预聚体按照如下方法制备而成:
(a)二异氰酸酯与羟基封端的聚硅氧烷反应得到异氰酸酯封端的齐聚物;
(b)再加入封端剂反应,熟化,即得;
所述二异氰酸酯、羟基封端的聚硅氧烷、封端剂的摩尔比为(1.2~2):1:(0.16~1.8),优选为(1.3~2):1:(0.52~1.34);
优选的,步骤(1)所述反应条件为:75~90℃反应2~4小时;
步骤(2)所述反应条件为:40~60℃反应1~3小时;所述熟化条件为:60~80℃熟化4~8小时。
更进一步地,上述二异氰酸酯选自二苯基甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI、间苯二甲基二异氰酸酯XDI、六亚甲基二异氰酸酯HDI、异佛尔酮二异氰酸酯IPDI、氢化4,4-二苯甲烷二异氰酸酯H12MDI中的一种或多种的混合物;
所述羟基封端的聚硅氧烷为羟基封端的聚二甲基硅氧烷;
所述封端剂为同时含有一个可与异氰酸酯反应的羟基和至少一个乙烯基的丙烯酸酯类化合物,优选为甲基丙烯酸羟乙酯、丙烯酸-2-羟乙酯、季戊四醇三丙烯酸酯中的一种或任意组合的混合物。
本发明还提供了一种增强3D打印硅橡胶制品的制备方法,使用上述的试剂盒制备,包括如下步骤:
(1)使用所述试剂盒的3D打印墨水通过UV辅助直书式3D打印得到3D打印硅橡胶制品;
(2)将步骤(1)得到的3D打印硅橡胶制品浸泡在所述增强剂溶液中浸泡1~2880min后,干燥即得;
优选的,步骤(2)所述的浸泡时间为15min。与现有技术相比,本发明的有益效果:
本发明开发了一种增强3D打印硅橡胶制品的方法,通过使用特定的浸泡用增强液体系,利用浸泡工艺将硅橡胶-聚脲的合成过程进行解离,设计到打印的不同阶段,无需对设备进行改造,回避了直接打印固态的硅橡胶-聚脲材料,解决了高模量硅橡胶-聚脲材料为固体无法进行室温3D直书写打印的问题;可以快速、简便地获得以高模量硅橡胶-聚脲材料的3D打印制品。
本发明术语:3D打印硅橡胶制品的增强液:是指能够通过浸泡将已经经过3D打印成型的制品的机械性能进一步提高的溶液。
官能团数量为2~4个的醇、胺或醇胺:指二元醇、三元醇、四元醇、二元胺、三元胺、四元胺,或含有羟基和胺基的醇胺,且醇胺的羟基数量和胺基数量之和为2、3或4个。
4,4'-亚甲基二(2-氯苯胺)缩写为MOCA、3,5-二甲硫基甲苯二胺缩写为DMTDA、3,5-二乙基甲苯二胺缩写为DETDA。
显然,根据本发明的上述内容,按照本领域的普通技术知识和惯用手段,在不脱离本发明上述基本技术思想前提下,还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式,对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
附图说明
图1是光固化硅橡胶预聚体及硅橡胶-聚脲材料室温下状态。
图2是本发明3D打印构件的简单立方结构示意图。
图3是本发明的UV辅助3D光固化墨水浸泡前后外观特性变化的比对。
具体实施方式
本发明实施例所用3D打印设备由实验室自主搭建,亦可购买市售UV辅助直书式3D打印机实现。其余所用原料与设备均为已知产品,通过购买市售产品所得。
实施例1、本发明增强3D打印硅橡胶制品的制备
1、光固化硅橡胶预聚体的制备
将羟基封端的聚二甲基硅氧烷(分子量为1000)与催化剂有机铋复配,缓慢加入装有二异氰酸酯的反应釜中(异氰酸酯指数=1.3),密封反应釜,打开搅拌,导入氮气进行以下过程;
升温至75~90℃,保温2~4小时;
降低温度至40~60℃,缓慢加入甲基丙烯酸羟乙酯,调节异氰酸酯指数至1.04,保温1~3小时
取出产物,60~80℃熟化4~8小时,得到光固化硅橡胶预聚体,其中乙烯基含量为1.03%;异氰酸酯含量为:0.32%(室温下状态如图1a所示,若直接用二元胺等扩链剂扩链反应制备成硅橡胶-聚脲材料,则如图1b所示,无法进行3D打印)。
2、3D打印墨水的配制
浸泡增强打印墨水的具体配方及各组分所占质量分数(%)如下:
准确称取各组分后,借助行星式搅拌器搅拌脱泡后备用。
3D打印制件的制备
选用500μm的针头,通过自主搭建的UV辅助直书式打印机在室温下打印具有简单立方结构(参见图2)的样品,打印层数为9层,线间距为1.8mm,制件长×宽×高为20mm×20mm×4.2mm,样品如图3a所示。
3、3D打印制件的浸泡增强
将步骤1中获得3D打印制件置于含有增强剂的溶液中浸泡,此处选用的增强剂为1,6-己二胺(HMDA),溶剂为异丙醇(IPA),配制浓度为0.3mmol/L,浸泡时长为15min。浸泡结束后,将制件移至烘箱中80℃干燥2h,最终样品如图3b所示。
实施例2、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中3D打印制件的浸泡时长改为1min,其余条件不变。
实施例3、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中3D打印制件的浸泡时长改为5min,其余条件不变。
实施例4、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中3D打印制件的浸泡时长改为30min,其余条件不变。
实施例5、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中3D打印制件的浸泡时长改为2880min,其余条件不变。
实施例6、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤1中3D打印制件的线间距修改为1.2mm,其余条件不变。
实施例7、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤1中3D打印制件的线间距修改为1.5mm,其余条件不变。
实施例8、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中用于浸泡3D打印制件的增强剂溶液的溶剂改为水,其余条件不变。
实施例9、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中用于浸泡3D打印制件的增强剂溶液的溶剂改为四氢呋喃(THF),其余条件不变。
实施例10、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中用于浸泡3D打印制件的增强剂溶液的溶剂改为N,N-二甲基乙酰胺(DMAc),其余条件不变。
实施例11、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中用于浸泡3D打印制件的增强剂溶液的配制浓度改为0.1mol/L,其余条件不变。
实施例12、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中用于浸泡3D打印制件的增强剂溶液的配制浓度改为0.15mol/L,其余条件不变。
实施例13、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中用于浸泡3D打印制件的增强剂溶液的配制浓度改为0.2mol/L,其余条件不变。
实施例14、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中用于浸泡3D打印制件的增强剂溶液的配制浓度改为0.25mol/L,其余条件不变。
实施例15、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中用于浸泡3D打印制件的增强剂改为乙二胺(EDA),其余条件不变。
实施例16、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中打印墨水配方中稀释剂的含量改为5%,其余条件不变。
实施例17、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤2中打印墨水配方中功能填料的含量改为5%,其余条件不变。
实施例18、本发明增强3D打印硅橡胶制品的制备
1、光固化硅橡胶预聚体的制备
将羟基封端的聚二甲基硅氧烷(分子量为1000)与催化剂有机铋复配,缓慢加入装有二异氰酸酯的反应釜中(异氰酸酯指数=2.0),密封反应釜,打开搅拌,导入氮气进行以下过程;
升温至75~90℃,保温2~4小时;
降低温度至40~60℃,缓慢加入甲基丙烯酸羟乙酯,调节异氰酸酯指数至1.33,保温1~3小时
取出产物,60~80℃熟化4~8小时,得到光固化硅橡胶预聚体,其中乙烯基含量为1.74%;异氰酸酯含量为2.70%。
2、3D打印墨水的配制
浸泡增强打印墨水的具体配方及各组分所占质量分数(%)如下:
准确称取各组分后,借助行星式搅拌器搅拌脱泡后备用。
3D打印制件的制备
选用500μm的针头,通过自主搭建的UV辅助直书式打印机在室温下打印具有简单立方结构(参见图1)的样品,打印层数为9层,线间距为1.8mm,制件长×宽×高为20mm×20mm×4.2mm。
3、3D打印制件的浸泡增强
将步骤2中获得3D打印制件置于含有增强剂的溶液中浸泡,此处选用的增强剂为1,6-己二胺,溶剂为异丙醇,配制浓度为0.3mmol/L,浸泡时长为15min。浸泡结束后,将制件移至烘箱中80℃干燥2h。
实施例19、本发明增强3D打印硅橡胶制品的制备
参照实施例1,将步骤1中制备预聚体的异氰酸指数改为1.2,加入甲基丙烯酸羟乙酯,调节异氰酸酯指数改为1.11,使所得光固化硅橡胶预聚体的乙烯基含量为0.35%;异氰酸酯含量为0.82%,其余条件不变。
实施例20、本发明增强3D打印硅橡胶制品的制备
参照实施例18,将步骤1中制备预聚体中加入甲基丙烯酸羟乙酯,调节异氰酸酯指数改为1.82,使所得光固化硅橡胶预聚体的乙烯基含量为0.37%;异氰酸酯含量为5.21%,其余条件不变。
实施例21本发明增强3D打印硅橡胶制品的制备
参照实施例18,将步骤1中制备预聚体中加入甲基丙烯酸羟乙酯,调节异氰酸酯指数改为1.05,使所得光固化硅橡胶预聚体的乙烯基含量为2.93%;异氰酸酯含量为0.51%,其余条件不变。
对比例1
参照实施例1,仅省略第3步浸泡操作(即3D打印制件的浸泡时长为0min),其余条件不变。
对比例2
1、光固化硅橡胶预聚体的制备
将羟基封端的聚二甲基硅氧烷(分子量为1000)与催化剂有机铋复配,缓慢加入装有二异氰酸酯的反应釜中(异氰酸酯指数=1.3),密封反应釜,打开搅拌,导入氮气进行以下过程;
升温至75~90℃,保温2~4小时;
降低温度至40~60℃,缓慢加入甲基丙烯酸羟乙酯,保温1~3小时,随后加入足量的甲醇,保温直至异氰酸酯基团被完全反应消耗。
取出产物,60~80℃熟化4~8小时,得到光固化硅橡胶预聚体,其中乙烯基含量为1.03%;异氰酸酯含量为0。
(与实施例1的区别在于预聚体中不含活性异氰酸酯基团)
2、3D打印墨水的配制
打印墨水的具体配方及各组分所占质量分数(%)如下:
准确称取各组分后,借助行星式搅拌器搅拌脱泡后备用3D打印制件的制备;
3D打印制件的制备:
选用500μm的针头,通过自主搭建的UV辅助直书式打印机在室温下打印具有简单立方结构(参见图1)的样品,打印层数为9层,线间距为1.8mm,制件长×宽×高为20mm×20mm×4.2mm。
3、3D打印制件的浸泡增强
将(2)中获得3D打印制件置于含有增强剂的溶液中浸泡,此处选用的增强剂为1,6-己二胺,溶剂为异丙醇,配制浓度为0.3mmol/L,浸泡时长为15min。浸泡结束后,将制件移至烘箱中80℃干燥2h。
对比例3
参照对比例2,仅省略第3步浸泡操作(即3D打印制件的浸泡时长为0min),其余条件不变。
以下通过实验例证明本发明的有益效果。
实验例1、本发明增强3D打印硅橡胶制品的性能表征
1、实验方法
实施例和对比例材料的压缩性能采用万能试验机进行测试,压缩速率设定为1.5mm/min;测试标准参照《GB/T 7757-2009硫化橡胶或热塑性橡胶压缩应力应变性能的测定》执行。
2、实验结果
如表1所示。表格参数说明:t表示浸泡时长;Pσ表示泡沫平台应力;σ为泡沫压缩应变为60%时对应的压缩强度;表示泡沫孔隙率;S表示溶剂;C表示增强剂浓度CE表示增强剂;I表示与对比例1相比,平台应力增加的幅度I=(Pσ(i)-Pσ(1))*100/Pσ(1),i为任意对应实施例或对比例序号。
表1硅橡胶-聚脲材料3D打印泡沫性能评价
由实施例1以及对比例1~3可以看出,本发明的增强策略可以实现3D打印硅橡胶制品的显著增强。
根据实施例1~5及对比例1的测试结果可以看出,在相同孔隙率条件下,浸泡后泡沫力学性能显著增加,且随着浸泡时长的增加,机械性能呈现增长趋势;总体而言,短时浸泡(1min)即可实现快速增强。
从实施例1、8~10可以看出,在相同增强剂浓度条件下,简单通过更换溶剂也可实现对泡沫力学性能的提升与调控,其中优选的IPA作为溶剂时增强效果最好。
从实施例1、11~14可以看出,相同浸泡时间下,随着增强剂浓度的提高,增强效果提升,优选增强剂浓度为0.3mmol/L。
对比实施例1、15可以看出,相同浸泡时间、浸泡浓度条件下,通过更换增强剂亦可实现对泡沫力学性能的提升,优选HMDA作为增强剂。
对比实施例1、6、7、15、18测试结果可以看出,本发明的增强策略在传统泡沫通过孔隙率调控机械性能的基础上,赋予了泡沫一种新的机械性能调控手段,即可通过浸泡及浸泡工艺参数的选择实现泡沫机械性能的增强。
综上所述,本发明成功开发了一种通过浸泡显著提升墨水材料机械性能的方法,实现了高模量硅胶-聚脲材料室温下的直书式3D打印。
Claims (10)
1.增强剂溶液作为3D打印硅橡胶制品的增强液的用途,其特征在于,所述增强剂是官能团数量为2~4个的醇、胺或醇胺,所述增强剂溶液的溶剂为甲醇、异丙醇、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、丙酮、二氯甲烷、氯仿、乙酸乙酯、甲苯、N-甲基吡咯烷酮中的一种或几种;
所述3D打印硅橡胶制品的材料包括含有异氰酸酯基的聚硅氧烷聚氨酯,所述聚硅氧烷聚氨酯中异氰酸酯基的含量为0.3~5.21wt%。
2.如权利要求1所述的用途,其特征在于,所述增强剂是乙二胺、1,6-己二胺、4,4'-亚甲基二(2-氯苯胺)、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、乙醇胺、二乙醇胺、三乙醇胺,优选为1,6-己二胺;
所述增强剂溶液的溶剂为异丙醇、水、四氢呋喃或N,N-二甲基乙酰胺;优选为异丙醇。
3.如权利要求1所述的用途,其特征在于,所述增强剂溶液中增强剂浓度为0.1~0.3mmol/L,优选为0.3mmol/L。
4.一种增强3D打印硅橡胶制品的制备试剂盒,其特征在于,由如下组分组成:
组分一:3D打印墨水;
组分二:增强剂溶液;
其中,3D打印墨水含有如下质量分数的原料:
光固化硅橡胶预聚体60~100%、光引发剂0.1~5%、活性稀释剂0~20%、功能填料0~40%;
所述光固化硅橡胶预聚体为含有乙烯基和异氰酸酯基的聚硅氧烷聚氨酯,乙烯基含量为0.35~2.93wt%,异氰酸酯基含量为0.3~5.21wt%;
增强剂溶液由如下原料组成:增强剂0.1~0.3mmol/L,余量为溶剂;
所述增强剂是官能团数量为2~4个的醇、胺或醇胺,所述溶剂为甲醇、异丙醇、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、丙酮、二氯甲烷、氯仿、乙酸乙酯、甲苯、N-甲基吡咯烷酮中的一种或几种。
5.如权利要求4所述的制备试剂盒,其特征在于,所述增强剂是乙二胺、1,6-己二胺、4,4'-亚甲基二(2-氯苯胺)、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、乙醇胺、二乙醇胺、三乙醇胺、甘油、三(2-氨基乙基)胺,优选为1,6-己二胺;
所述增强剂溶液的溶剂为异丙醇、水、四氢呋喃或N,N-二甲基乙酰胺;优选为异丙醇。
6.如权利要求4所述的制备试剂盒,其特征在于,所述增强剂浓度为0.3mmol/L。
7.如权利要求4~6任一项所述的制备试剂盒,其特征在于,所述光固化硅橡胶预聚体的数均分子量为500~8000;
所述光引发剂为安息香双甲醚、2-羟基-2-甲基苯丙酮、2,4,6-三甲基苯甲酰基二苯基氧化膦,2-异丙基硫化杂蒽酮,二酰基膦氧化物、1-羟基-环己基-苯基甲酮中的一种或几种;
所述活性稀释剂是二异氰酸酯或丙烯酸酯类化合物,所述二异氰酸酯为:二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、间苯二甲基二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、氢化4,4-二苯甲烷二异氰酸酯中的一种或任意组合的混合物;
所述丙烯酸酯类化合物为:丙烯酸丁酯、丙烯酸十二醇酯、丙烯酸十六醇酯、丙烯酸异冰片酯、甲基丙烯酸羟乙酯、三丙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二季戊四醇丙烯酸酯中的一种或几种;
所述功能填料为白炭黑、炭黑、碳纳米管、石墨烯中的一种或几种。
8.如权利要求7所述的试剂盒,其特征在于,所述光固化硅橡胶预聚体按照如下方法制备而成:
(a)二异氰酸酯与羟基封端的聚硅氧烷反应得到异氰酸酯封端的齐聚物;
(b)再加入封端剂反应,熟化,即得;
所述二异氰酸酯、羟基封端的聚硅氧烷、封端剂的摩尔比为(1.2~2):1:(0.16~1.8);
优选的,步骤(1)所述反应条件为:75~90℃反应2~4小时;
步骤(2)所述反应条件为:40~60℃反应1~3小时;所述熟化条件为:60~80℃熟化4~8小时。
9.如权利要求8所述的试剂盒,其特征在于,所述二异氰酸酯选自二苯基甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI、间苯二甲基二异氰酸酯XDI、六亚甲基二异氰酸酯HDI、异佛尔酮二异氰酸酯IPDI、氢化4,4-二苯甲烷二异氰酸酯H12MDI中的一种或多种的混合物;
所述羟基封端的聚硅氧烷为羟基封端的聚二甲基硅氧烷;
所述封端剂为同时含有一个可与异氰酸酯反应的羟基和至少一个乙烯基的丙烯酸酯类化合物,优选为甲基丙烯酸羟乙酯、丙烯酸-2-羟乙酯、季戊四醇三丙烯酸酯中的一种或任意组合的混合物。
10.一种增强3D打印硅橡胶制品的制备方法,其特征在于,使用权利要求4所述的试剂盒制备,包括如下步骤:
(1)使用所述试剂盒的3D打印墨水通过UV辅助直书式3D打印得到3D打印硅橡胶制品;
(2)将步骤(1)得到的3D打印硅橡胶制品浸泡在所述增强剂溶液中浸泡1~2880min后,干燥即得;
优选的,步骤(2)所述的浸泡时间为15min。
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