CN117460613A - 生产三维打印制品的方法 - Google Patents
生产三维打印制品的方法 Download PDFInfo
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- CN117460613A CN117460613A CN202280041833.5A CN202280041833A CN117460613A CN 117460613 A CN117460613 A CN 117460613A CN 202280041833 A CN202280041833 A CN 202280041833A CN 117460613 A CN117460613 A CN 117460613A
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- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本发明涉及利用可光固化有机硅组合物来生产三维(3D)打印制品的方法,所述组合物包含含有特定(甲基)丙烯酸酯基团作为端基的有机硅。
Description
技术领域
本发明涉及使用包含(甲基)丙烯酸酯有机硅聚合物的可光固化组合物来生产三维(3D)打印制品的方法。
背景技术
3D打印技术(又称为增材制造(AM)、快速成型(rapid prototyping)或分层制造)涵盖多种不同的技术,并且用于创建具有几乎任何形状或几何结构的三维物体,而不需要模具或机加工。现今,增材制造正经历非常强的动力,并且由于众多可能的商业应用而具有重要的增长潜力。为了增加其使用,有必要拓宽可配合增材制造设备使用的材料的范围。
一类重要的可固化有机硅组合物通过热固性交联来固化,它们配合3D打印机的使用是复杂的并且几乎不与增材制造过程相容。实际上,在逐层3D打印过程中,每个层必须保持其形状。随着产品的高度增加,下层不保持其形状并流动,从而导致构建结构的变形或坍塌。因此,获得了具有不合适形状的有机硅部件。
已制定了几种解决方案来规避此适印性问题。例如,在WO2018/206689中,经由3D液相沉积建模过程、利用具有适当流变性质的可固化有机硅组合物实现了有机硅3D打印物体,从而避免了在室温下完全固化前打印物体的坍塌或变形。这种方法的主要缺陷是缺乏过程精确性(>100微米/层),并且需要进行成品物体的后处理以确保固化过程完全结束。
现在,对基于光聚合的3D打印技术的关注正在增加。它们由液体材料开始,局部沉积并使其固化或从液槽使其选择性固化。这类技术的实例是UV立体光刻(SLA)、UV数字光处理(DLP)、连续液体界面生产(CLIP)、UV挤出和喷墨沉积。
UV立体光刻(SLA)例如公开于WO2015197495中。例如,UV立体光刻(SLA)使用激光束,其通常经扫描仪系统在X-Y(水平)平面中移动。电机被来自生成数据源的信息引导,驱动反射镜在表面上发送激光束。
UV数字光处理(DLP)例如公开于WO2016181149和US20140131908中。在UV数字光处理(DLP)中,3D模型被发送至打印机,并且在安全灯条件下,液体聚合物槽暴露于来自DLP投影仪的光。DLP投影仪将3D模型的图像显示于液体聚合物上。DLP投影仪可安装在可由透明弹性体膜制成的窗口下,来自DLP投影仪的UV光透过该膜照射。
连续液体界面生产(CLIP,原名连续液体中间相打印)例如公开于WO2014126837和WO2016140891中,其例如使用光聚合以创建具有各种形状的光滑面的固态物体。
挤出3D打印方法例如公开于WO2015107333、WO2016109819和WO2016134972中。例如,在此方法中,经过喷嘴挤出材料以打印物体的一个截面,对于每个层可重复此举。能量源可直接附接至喷嘴使得立刻在挤出之后即时固化,或可与喷嘴分离以延迟固化。喷嘴或构建平台通常在X-Y(水平)平面中移动,之后一旦完成了每个层,则在Z轴(垂直)平面中移动。可在沉积后立即UV固化,或版(plate)在UV光下移动以给出沉积与UV固化之间的延迟。可使用支撑材料来避免在空气中挤出细丝材料。可使用一些后加工处理来改进打印表面的品质。
喷墨沉积例如公开于WO201740874、WO2016071241、WO2016134972、WO2016188930、WO2016044547和WO2014108364中,其例如使用具有在打印区域周围移动、喷射特定的液态可固化组合物(例如通过UV聚合)的打印头的材料喷射打印机。喷墨喷嘴形成液滴的能力以及其容积和其速度受材料的表面张力影响。
因为3D光聚合是基于使用可在暴露于特定波长的光源中固化/光聚合的液态单体/低聚物,可光固化有机硅组合物由于其固化材料的许多优点是极具吸引力的,优点为诸如柔性、生物相容性、对于电气组件和电子组件的绝缘性质,以及良好的耐化学性、耐温性和耐候性。
现今在3D打印中使用的可光固化液态有机硅组合物主要是偶联至可光活化催化剂的加聚可固化有机硅组合物。此技术的问题是反应的催化是非瞬时的,并且在使用例如3D喷墨打印时固化产品通常需要后固化。
另一种新的方式描述于US2020071525中,其中描述了用于制造立体光刻3D打印有机硅结构的可光固化聚(硅氧烷)组合物,包含:
(a)具有第一端基有机官能和第二端基有机官能的第一可聚合聚(硅氧烷),每个端基包含丙烯酸酯基团或甲基丙烯酰氧基丙基基团;
(b)包含重复单元的第二可聚合聚(硅氧烷),该重复单元中的至少一些具有侧链可聚合基团;
(c)光引发剂,其优选为(2,4,6-三甲基苯甲酰基)苯基亚膦酸乙酯(TPO-L);和
(d)敏化剂,其优选为异丙基噻吨酮(ITX)。
具体而言,含有甲基丙烯酰氧基丙基端基的优选组分(a)具有下式:
其具有约10kDa至约60kDa的优选分子量。其被描述为适合于构建微型器件,并且3D打印结构优选具有0.5-1MPa量级的低杨氏模量和约140%的断裂伸长率。通过使光引发剂浓度的含量升至约0.8%(以组合物总重量计的重量%)获得了最大约160%的断裂伸长率。然而,在此含量下在固化后光引发剂引起黄色材料,这在许多应用中是不期望的。此外,所有实例都包括使用异丙基噻吨酮(ITX)作为敏化剂。
因此,仍需要由有机硅光聚合物组合物获得3D物体,其给出了固化产物更高的、具体而言远高于上文参考文献中所述的140%的断裂伸长性质,适于立式(stand)3D UV打印技术诸如UV立体光刻(SLA)、UV数字光处理(DLP)、连续液体界面生产(CLIP)、UV挤出和喷墨沉积。此外,还需要改进拉伸强度和其它物理性质,以开启其在各个领域诸如医疗保健、电子、航空航天、运输、建筑、工业备件、用垫圈密封和粘合的使用。
本发明的目的是提供利用可光固化有机硅组合物生产三维打印制品的方法,其给出了固化产物的更高的、具体而言远高于现有技术中所述的140%的断裂伸长性质,并且具有改进的拉伸强度和其它物理性质,以开启可光固化有机硅组合物在3D打印中的使用,用于各个领域诸如医疗保健、电子、航空航天、运输、建筑、工业备件、用垫圈密封和粘合等。
本发明的另一个目的是提供利用可光固化有机硅组合物生产三维打印制品的方法,该组合物不必然需要使用敏化剂诸如异丙基噻吨酮(ITX)。
本发明的另一个目的是提供根据本发明的方法形成的三维(3D)打印制品。
这些目的尤其通过本发明实现,其涉及包括以下的生产三维打印制品的方法:
1)提供包含以下的可光固化组合物X:
(a)100重量份的至少一种具有下式(1)的有机聚硅氧烷聚合物CE:
M*Dx M*(1)
其中:
·M*为R1(R)2SiO1/2;
·D为(R)2SiO2/2;
·x≥60,优选60≤x≤500,且最优选90≤x≤400;
·R为选自由甲基、乙基、丙基、三氟丙基组成的组的烷基和苯基,且最优选R为甲基;
·R1为具有通式-CnH2nO-CH2CHR2(CH2)m-OCOCH=CHR3的结构部分,其中n为3或4且m为0或1、且优选m为1,R2为H、OH或-CzH2z-CH2OH,z为0、1、2或3,且R3为H或-CH3;
(b)0至20重量份、优选1至20重量份且甚至更优选1至10重量份的至少一种具有下式(2)的有机聚硅氧烷聚合物XL:
MDv(DACR)wM (2)
其中:
·M为R2(R)2SiO1/2、(R)3SiO1/2或R4(R)2SiO1/2;
·D为(R)2SiO2/2;
·DACR为(R2)(R)SiO2/2;
·y为0至500,优选10至500,且最优选50至400;
·w为0至50,优选1至25,且最优选3至20;并且当w=0时,y为1至500且M表示R2(R)2SiO1/2或R4(R)2SiO1/2;
·R为选自由甲基、乙基、丙基、三氟丙基组成的组的烷基和苯基,且最优选R为甲基;
·R2为具有以下通式的结构部分:
ο-CnH2nO-CH2CHR2(CH2)m-OCOCH=CHR3,其中n为3或4且m为0或1,m为0或1,R2为H、OH或-CzH2z-CH2OH,z为0、1、2或3,且R3为H或-CH3;或
ο-CnH2nO-COCH=CHR3,其中n为3或4且R3为H或-CH3;
·R4为具有式(3)的结构部分:
(c)0.01至10重量份、优选0.01至3重量份的至少一种光引发剂PI,
(d)至少15重量份、优选20至100重量份、且甚至更优选20至50重量份的至少一种无机填料F,
(e)0至10重量份的至少一种敏化剂PS,
(f)0至10000重量份的至少一种可光固化有机(甲基)丙烯酸酯单体/低聚物M,和
(g)0至10重量份的至少一种添加剂I,
2)使可光固化组合物X暴露于光化辐射以在版或支撑物上形成固化截面,并且
3)在先前的固化截面上用新层重复步骤1)和2)以构建三维打印制品。
为了实现这些目的,值得称赞的是,申请人完全令人惊讶地且出乎意料地证明了,对比根据现有技术的标准丙烯酸酯化封端的有机硅((甲基)丙烯酰氧基丙基端基),通过在所述可光固化组合物X中使用特定的丙烯酸酯化封端的有机硅(根据本发明的3-丙烯酰氧基-2-羟基丙氧基丙基端基)与至少15重量份(相对于100重量份的丙烯酸酯化封端的有机硅)的无机填料组合,可经由3D UV打印获得固化材料,该材料具有远高于现有技术中所述的140%的更高的断裂伸长性质、良好的拉伸强度和其它物理性质的一些改进,以开启可光固化有机硅组合物在3D打印中的使用,用于各个领域诸如医疗保健、电子、航空航天、运输、建筑、工业备件、用垫圈密封和粘合等。在不使用敏化剂诸如异丙基噻吨酮(ITX)下获得了该结果,这允许3D打印过程有更多灵活性,可使用更广范围的3D UV打印机。
在优选的实施方案中,根据本发明的有机聚硅氧烷聚合物CE具有4000g/mol至40000g/mol、优选5700g/mol至30000g/mol、且甚至更优选5700g/mol至24000g/mol的平均分子量。
在另一个优选的实施方案中,选择组分和组分的量以使组合物X具有在25℃下低于50Pa·s且优选在25℃下低于20Pa·s的动态粘度。在这种情况下,可通过常用的SLA打印机或DLP打印机诸如ASIGA MAX来加工组合物X。
术语“动态粘度”意指材料中伴随流动速率梯度存在的剪切应力。本报告中提及的所有粘度都对应于在25℃下以本身已知的方式或根据标准ASTM D445测量的动态粘度的数值。粘度通常使用Brookfield粘度计测量。
在优选的实施方案中,有机聚硅氧烷聚合物CE包含含有羟基的(甲基)丙烯酸酯结构部分作为端基,并具有平均通式:
M*Dx M*
其中:
·M*为R1(R)2SiO1/2;
·D为(R)2SiO2/2;
·x≥60,优选60≤x≤500,且最优选90≤x≤400;
·R为选自由甲基、乙基、丙基、三氟丙基组成的组的烷基和苯基,且最优选R为甲基;
·R1为具有通式-CnH2nO-CH2CHR2(CH2)m-OCOCH=CHR3的结构部分,其中n为3或4且m为0或1,m为0或1,R2为OH或-CzH2z-CH2OH,z为1、2或3,且R3为H或-CH3。
在另一个优选的实施方案中,有机聚硅氧烷聚合物CE(具有3-丙烯酰氧基2-羟基丙氧基丙基端基的聚二甲基硅氧烷)具有下式(4):
其中n≥60,且优选60≤n≤500,且最优选80≤n≤400。
在优选的实施方案中,有机聚硅氧烷聚合物XL选自由聚合物(5)至(8)组成的组:
其中a为1至20,且优选a为1至10;b为1至500,且优选b为10至500;
其中n为10至400,优选n为50至200,且甚至更优选n为50至150;
其中n为1至500,且优选n为1至200;
其中a为2至50,且优选a为2至20;b为0至500,且优选b为10至400。
光引发剂的合适的实例包括酰基磷氧化物或酰基膦氧化物。可使用溶剂诸如异丙醇(IPA)与光引发剂组合以使其溶于有机硅组合物中。
根据本发明的合适的光引发剂是Norrish I型的那些,其在用UV光能辐照时裂解产生自由基。优选的光引发剂是膦氧化物的衍生物,诸如:
(9)二苯基(2,4,6-三甲基苯甲酰基)氧化膦(TPO)
(10)(2,4,6-三甲基苯甲酰基)苯基亚膦酸乙酯(TPO-L)
(11)苯基双(2,4,6-三甲基苯甲酰基)氧化膦(BAPO)
CPO-1和CPO-2可根据Molecules 2020,25(7),1671,New Phosphine Oxides asHigh Performance Near UV Type IPhotoinitiators of Radical Polymerization中所述方案来制备。
其它合适的光引发剂是诸如US2016/0168177A1中所述的液态二酰基膦氧化物或诸如US2008/0004464中所述的酰基膦。
最优选的光引发剂是(2,4,6-三甲基苯甲酰基)苯基亚膦酸乙酯(10)(TPO-L)。
合适的无机填料F可选自由增强无机填料F1、导热无机填料F2、导电无机填料F3和它们的混合物组成的组。
在一些实施方案中,增强无机填料F1选自二氧化硅和/或氧化铝,优选选自二氧化硅。作为可使用的二氧化硅,设想填料特征为通常小于或等于0.1μm的细粒度,和高的比表面积与重量之比(通常位于约50m2/g至大于300m2/g的范围内)。此类型的二氧化硅是可商购获得的产品,并且在制造有机硅组合物的领域中是众所周知的。这些二氧化硅可为胶态二氧化硅、热解制备的二氧化硅(称作燃烧二氧化硅或气相二氧化硅)或通过湿法制备的二氧化硅(沉淀二氧化硅),或这些二氧化硅的混合物。出于本发明的目的,能够形成无机填料的二氧化硅的化学性质和制备方法并不重要,只要二氧化硅对打印产品具有增强作用即可。当然还可使用各种二氧化硅的切段(cuts)。这些二氧化硅粉末具有通常接近或等于0.1μm的平均粒度,和大于50m2/g、优选50至400m2/g、尤其是150至350m2/g的BET比表面积5。借助于至少一种选自满足至少以下两个标准的分子的组的增容剂来任选地预处理这些二氧化硅:
a)在其氢键区中具有与二氧化硅的高相互作用(与自身和与周围硅油);并且
b)自身或其降解产物易于通过在真空下在气流中加热从最终混合物中除去,并且具有低分子量的化合物是优选的。
这些二氧化硅也可通过添加未处理的二氧化硅和至少一种具有类似于可在预处理中使用且如上文定义的性质的增容剂来原位处理。
根据处理方法(预处理或原位)来选择增容剂,并且可例如选自包含以下的组:氯硅烷;聚有机环硅氧烷,诸如八甲基环硅氧烷(D4);硅氮烷,优选二硅氮烷,或它们的混合物;六甲基二硅氮烷(HMDZ)是优选的硅氮烷,且其可与二乙烯基四甲基二硅氮烷结合;每分子具有一个或多个连接至硅的羟基的聚有机硅氧烷;胺,诸如氨或具有低分子量的烷基胺诸如二乙胺,烷氧基硅烷诸如甲基丙烯酰氧基丙基三甲氧基硅烷;具有低分子量的有机酸,诸如甲酸或乙酸、或丙烯酸,以及它们的混合物。在原位处理的情况下,优选在水的存在下使用增容剂。对于此方面的更多细节,可例如参考专利FR-B-2 764 894。
可使用现有技术的增容方法,用硅氮烷提供早期处理(例如FR-A-2 320 324)或延迟处理(例如EP-A-462 032),要记住根据使用的二氧化硅,它们的使用通常不可获得通过在根据本发明的两种场合下处理获得的在机械性质、特别是伸展性方面的最佳结果。
在优选的实施方案中,无机填料F选自由胶态二氧化硅、气相二氧化硅、沉淀二氧化硅或它们的混合物组成的组。
作为增强无机填料F1的实例,可使用氧化铝,且特别是有利地采用可高度分散的、以已知方式掺杂或不掺杂的氧化铝。当然还可使用各种氧化铝的切段。优选地,所用增强填料是单独或与氧化铝混合的燃烧二氧化硅。
根据本发明可设想使用互补填料诸如导热无机填料F2和/或导电无机填料F3。二者都可用表面积改性剂进行表面处理,使用该改性剂来控制填料形状的形态和/或填充填料的内部空隙/孔隙。引入表面积改性剂使填料的总表面积减小。
合适的导热无机填料F2包括:氮化硼,氮化铝,铜,银,铝,镁,黄铜,金,镍,氧化铝,氧化锌,氧化镁,氧化铁,氧化银,氧化铜,金属涂覆的有机颗粒,镀银镍,镀银铜,镀银铝,镀银玻璃,银片,银粉,炭黑,石墨,金刚石,碳纳米管,二氧化硅,和它们的混合物。优选地,导热无机填料F2是氮化硼。
合适的导电无机填料F3包括金属或其它组分。具体而言,其可包括例如:填料,诸如炭黑、石墨;金属组分,诸如铝、铜、黄铜、青铜、镍或铁;导电无机颜料,诸如氧化锡、氧化铁和二氧化钛;无机盐;以及它们的组合。特别有用的是石墨,且特别是合成石墨。其还可包括合成石墨、天然石墨和它们的组合。具体实施方案还可包括银颗粒、银涂覆的芯颗粒和碳纳米管。
当存在时,敏化剂PS在1ppm到至多10重量份的范围内。最优用量是在组合物X的全部含量的10至100ppm的范围内。
敏化剂意指吸收光能并通过将此能量转移至受体分子而作为给体的分子。
合适的敏化剂PS的实例包括由以下组成的组:二苯甲酮及其衍生物,噻吨酮及其衍生物,蒽醌及其衍生物,甲酸苄酯,樟脑醌,苯偶酰,菲醌,香豆素和乙酰香豆素(cetocoumarine),以及它们的混合物。
二苯甲酮衍生物意指取代的二苯甲酮和聚合版的二苯甲酮。术语“噻吨酮衍生物”指取代的噻吨酮,且蒽醌衍生物指取代的蒽醌、特别是蒽醌磺酸和丙烯酰胺基取代的蒽醌。
作为合适的敏化剂PS的具体实例,可具体地提及以下产品:异丙基噻吨酮,二苯甲酮,樟脑醌,9-呫吨酮,蒽醌,1,4-二羟基蒽醌,2-甲基蒽醌,2,2'-双(3-羟基-1,4-萘醌),2,6-二羟基蒽醌,1-羟基环己基-苯基酮,1,5-二羟基蒽醌,1,3-二苯基-1,3-丙二酮,5,7-二羟基黄酮,过氧化二苯甲酰,2-苯甲酰苯甲酸,2-羟基-2-甲基苯丙酰酮,2-苯基苯乙酮,蒽酮,4,4'-二甲氧基苯偶姻,菲醌,2-乙基蒽醌,2-甲基蒽醌,2-乙基蒽醌,1,8-二羟基蒽醌,过氧化二苯甲酰,2,2-二甲氧基-2-苯基苯乙酮,苯偶姻,2-羟基-2-甲基苯丙酮,苯甲醛,4-(2-羟基乙氧基)苯基-(2-羟基-2-甲基丙)酮,苯甲酰丙酮,(2,4,6-三甲基苯甲酰基)苯基亚膦酸乙酯,和它们的混合物。
作为敏化剂PS的可商购产品的实例,可提及以下产品:TZT,MBP,/>BP和噻吨酮衍生物,/>907,/>TX和TX-1产品。
其它实例包括WO2018/234643中描述的氧杂蒽酮或取代的噻吨酮类型的化合物和以下化合物(14)至(30):
/>
作为根据本发明可用的二苯甲酮的另一个实例,可提及化合物(31):
此化合物对应于产品Ebecryl P36(CAS:85340-63-2)。
当存在可光固化有机(甲基)丙烯酸酯单体/低聚物M时,其可用于添加上文所述的敏化剂。
合适的可光固化有机(甲基)丙烯酸酯单体/低聚物M的实例包括但不限于以下:聚乙二醇二丙烯酸酯(PEGDA),1,6-双-(甲基丙烯酰氧基-2-乙氧基羰基氨基)-2,4,4-三甲基己烷(UDMA),三乙二醇二甲基丙烯酸酯(TEGDMA),双酚A-甲基丙烯酸缩水甘油酯或2,2-双-[4-(2-羟基-3丙烯酸氧基丙氧基)苯基)丙烷(Bis-GMA),三羟甲基丙烷三丙烯酸酯(TTA)和双酚A乙氧基化二丙烯酸酯(Bis-EDA)。
本发明的可固化有机硅组合物可任选地包含至少一种添加剂I,只要它们不妨碍固化机制或不利地影响目标性质。根据其中所述组合物用于的应用和所需的性质选择所述添加剂。其可包括单独或作为混合物使用的各种类型的添加剂,诸如颜料、消光剂、热稳定剂和/或光稳定剂、抗静电剂、阻燃剂、抗细菌剂、抗真菌剂和触变剂。
在优选的实施方案中,选择组分(a)至(g)的成分和量以使组合物X具有在25℃下低于50Pa·s且优选在25℃下低于20Pa·s的动态粘度,以允许易于配合标准UV-3D打印机使用。
在优选的实施方案中,经由3D打印机,使用选自由UV立体光刻(SLA)、UV数字光处理(DLP)、连续液体界面生产(CLIP)、喷墨沉积和UV挤出组成的组的技术提供可光固化组合物X。这些技术和相关3D打印设备是本领域技术人员众所周知的。
为了构建物体,例如经由CAD软件(诸如SolidWorks、Sculpt或SelfCAD)使用3D数字文件。这些文件(通常是STL文件)经切片机(其将模型切成薄层以打印)处理。然后将指令发送至3D打印机。
将在阅读以下实施例时显现本发明的其它优点和特征,实施例以例示方式给出且决不是限制性的。
实施例
I)实施例中所用的原料:
1)具有双(3-丙烯酰氧基2-羟基丙氧基丙基)端基的聚二甲基硅氧烷CE:
聚二甲基硅氧烷聚合物CE-1(比较):n=6,在25℃下粘度170mPa·s,
聚二甲基硅氧烷聚合物CE-2(比较):n=45,在25℃下粘度200mPa·s,
聚二甲基硅氧烷聚合物CE-3(发明):n为250至280,在25℃下粘度1200mPa·s。
2)具有双(丙烯酰氧基丙基)端基的聚二甲基硅氧烷CE(比较):
聚二甲基硅氧烷聚合物CE-4(比较):n=130,粘度430mPa·s。
3)在链中具有(丙烯酰氧基-2-羟基丙氧基丙基)基团的聚二甲基硅氧烷XL:
聚二甲基硅氧烷聚合物XL-1:a为3至4且b为约220,
聚二甲基硅氧烷聚合物XL-2:a为7至8且b为约80。
4)聚合物XL-3:n=95,
5)在链中具有(3-丙烯酰氧基2-羟基丙氧基丙基)端基的聚二甲基硅氧烷XL-4(其中a为2至3且b为140至170):
(5)
6)无机填料F1:表面处理(三甲基硅氧基)的热解二氧化硅,由Wacker以商标名H2000销售。
7)光引发剂PI:
TPO-L:2,4,6-三甲基苯甲酰基二苯基亚膦酸酯,
BAPO:苯基双(2,4,6-三甲基苯甲酰基)氧化膦,
TPO:2,4,6-三甲基苯甲酰基二苯基氧化膦。
8)溶剂:IPA=异丙醇。
9)添加剂:Kri-Color Trans颜料(颜料)。
II)物理性质
粘度:样品的粘度是在25℃下根据ASTM D445或ISO3104测量的。
硬度:固化样品的硬度是在25℃下根据ASTM D2240或ISO868测量的。
拉伸强度和断裂伸长率:基于可固化有机硅组合物的固化样品的拉伸强度和断裂伸长率是在25℃下根据ASTM D412或ISO37测量的。
撕裂强度:固化样品的撕裂强度是在25℃下根据ASTM D624或ISO34-1测量的。
III)配方(固化并用3D打印机Asiga 3D打印)
配方是根据表1、2、3或4制备的。
然后手动或用快速混合器混合它们。然后将所得混合物倒入Asiga 3D打印机的槽中,该打印机具有1升的容量且具有XYZ 119×67×75mm的印刷版(printing plate)。然后设计了H2试样(长40mm+/-0.5,厚2mm+/-0.2)的“.stl”文件。利用“.stl”文件和27层的构建程序制备了2mm厚的试样。每层具有75微米的厚度。在385nm和5.8mW/cm2下,辐照第一层30s以实现对平台良好的粘附,且对后续的层每层辐照20s。在3D打印后,可在UV箱中将试样在405nm下正面/反面后固化180s。
物理性质引用于下表中。
表1:配方和物理性质(重量%)
表2:配方和物理性质(重量%)
实施例4(比较)对比实施例5至8(根据本发明)的比较显示出,通过使用根据本发明的特定丙烯酸酯化封端的有机硅(丙烯酰氧基丙氧基丙基端基)与至少15重量份(相对于100重量份的丙烯酸酯化封端的有机硅)的无机填料组合,可经由3D UV光打印获得固化材料,该材料具有远高于现有技术中所述的140%的更高的断裂伸长性质,且当存在上述填料时具有非常好的拉伸强度和撕裂性质。
表3:配方和在5mW/cm2下的物理性质(重量%)
实施例9与10之间的比较显示出,与现有技术中使用的具有丙烯酰氧基丙基端基的标准聚二甲基硅氧烷CE-4相比,本发明中使用的具有(丙烯酰氧基丙氧基丙基)端基的聚二甲基硅氧烷CE-3已在断裂伸长性质方面显示出更优(+30%)的性质(即使没有无机填料)。
表4:配方和物理性质(重量%)
在表4中,利用具有丙烯酸酯基团(交联剂)的各种聚二甲基硅氧烷,可获得优异的断裂伸长性质。
Claims (8)
1.生产三维打印制品的方法,包括:
(a)100重量份的至少一种具有下式(1)的有机聚硅氧烷聚合物CE:
M*Dx M*(1)
其中:
·M*为R1(R)2SiO1/2;
·D为(R)2SiO2/2;
·x≥60,优选60≤x≤500,且最优选90≤x≤400;
·R为选自由甲基、乙基、丙基、三氟丙基组成的组的烷基和苯基,且最优选R为甲基;
·R1为具有通式-CnH2nO-CH2CHR2(CH2)m-OCOCH=CHR3的结构部分,其中n为3或4且m为0或1、优选m为1,R2为H、OH或-CzH2z-CH2OH,z为1、2或3,且R3为H或-CH3;
(b)0至20重量份、优选1至20重量份且甚至更优选1至10重量份的至少一种具有下式(2)的有机聚硅氧烷聚合物XL:
M Dv(DACR)w M(2)
其中:
·M为R2(R)2SiO1/2、(R)3SiO1/2或R4(R)2SiO1/2;
·D为(R)2SiO2/2;
·DACR为(R2)(R)SiO2/2;
·y为0至500,优选10至500,且最优选50至400;
·w为0至50,优选1至25,且最优选3至20;并且当w=0时,y为1至500且M表示R2(R)2SiO1/2或R4(R)2SiO1/2;
·R为选自由甲基、乙基、丙基、三氟丙基组成的组的烷基和苯基,且最优选R为甲基;
·R2为具有以下通式的结构部分:
○-CnH2nO-CH2CHR2(CH2)m-OCOCH=CHR3,其中n为3或4且m为0或1,m为0或1,R2为H、OH或-CzH2z-CH2OH,z为1、2或3,且R3为H或-CH3;或
○-CnH2nO-COCH=CHR3,其中n为3或4且R3为H或-CH3;
·R4为具有式(3)的结构部分:
(c)0.01至10重量份、优选0.01至3重量份的至少一种光引发剂PI,
(d)至少15重量份、优选20至100重量份、且甚至更优选20至50重量份的至少一种无机填料F,
(e)0至10重量份的至少一种敏化剂PS,
(f)0至10000重量份的至少一种可光固化有机(甲基)丙烯酸酯单体/低聚物M,和
(g)0至10重量份的至少一种添加剂I;
2)使所述可光固化组合物X暴露于光化辐射以在版或支撑物上形成固化截面,并且
3)在先前的固化截面上用新层重复步骤1)和2)以构建所述三维打印制品。
2.根据权利要求1所述的方法,其中根据本发明的所述有机聚硅氧烷聚合物CE具有4000g/mol至40000g/mol、优选5700g/mol至30000g/mol、且甚至更优选5700g/mol至24000g/mol的平均分子量。
3.根据权利要求1所述的方法,其中所述有机聚硅氧烷聚合物CE包含含有羟基的(甲基)丙烯酸酯结构部分作为端基,并具有平均通式:
M*Dx M*
其中:
·M*为R1(R)2SiO1/2;
·D为(R)2SiO2/2;
·x≥60,优选60≤x≤500,且最优选90≤x≤400;
·R为选自由甲基、乙基、丙基、三氟丙基组成的组的烷基和苯基,且最优选R为甲基;
·R1为具有通式-CnH2nO-CH2CHR2(CH2)m-OCOCH=CHR3的结构部分,其中n为3或4且m为0或1,m为0或1,R2为OH或-CzH2z-CH2OH,z为1、2或3,且R3为H或-CH3。
4.根据权利要求1所述的方法,其中所述有机聚硅氧烷聚合物CE(具有3-丙烯酰氧基2-羟基丙氧基丙基端基的聚二甲基硅氧烷)具有下式(4):
其中n≥60,且优选60≤n≤500,且最优选80≤n≤400。
5.根据权利要求1所述的方法,其中所述有机聚硅氧烷聚合物XL选自由聚合物(5)至(8)组成的组:
其中a为1至20,且优选a为1至10;b为1至500,且优选b为10至500;
其中n为10至400,优选n为50至200,且甚至更优选n为50至150;
其中n为1至500,且优选n为1至200;
其中a为2至50,且优选a为2至20;b为0至500,且优选b为10至400。
6.根据权利要求1所述的方法,其中所述无机填料F选自由胶态二氧化硅、气相二氧化硅、沉淀二氧化硅或它们的混合物组成的组。
7.根据权利要求1所述的方法,其中选择所述组分和组分的量以使所述组合物X具有在25℃下低于50Pa·s且优选在25℃下低于20Pa·s的动态粘度。
8.根据权利要求1所述的方法,其中经由3D打印机,使用选自由UV立体光刻(SLA)、UV数字光处理(DLP)、连续液体界面生产(CLIP)、喷墨沉积和UV挤出组成的组的技术提供所述可光固化组合物X。
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