CN109789693A - 组成受控的共聚物的3d打印 - Google Patents

组成受控的共聚物的3d打印 Download PDF

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Publication number
CN109789693A
CN109789693A CN201780059439.3A CN201780059439A CN109789693A CN 109789693 A CN109789693 A CN 109789693A CN 201780059439 A CN201780059439 A CN 201780059439A CN 109789693 A CN109789693 A CN 109789693A
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China
Prior art keywords
composition
printing
control
computer
liquid
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Inventor
孙继润
李勇
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Ida Foundation
American Dental Association Health Foundation
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Ida Foundation
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Abstract

一种使用3D打印形成组成受控的产品的计算机控制的方法，其包括将两种或更多种液体反应物组合物沉积在相应的两个或多个储存器中；以及将所述两种或更多种液体反应物组合物混合，其又包括通过所述计算机控制所述混合的两种或更多种液体反应物组合物的质量比。所述计算机控制的方法进一步包括在所述计算机的控制下在基底之上扫描混合液体反应物喷嘴；将所述混合液体反应物组合物沉积在所述基底上；以及在所述计算机的控制下，操作光源以使所述沉积的混合液体反应物组合物聚合。

Description

组成受控的共聚物的3D打印
背景技术
使用聚合的三维打印是已知的。例如，Charles Hull的美国专利4,575,330公开了一种用于液体迭代聚合的系统。然而，Hull专利的系统产生具有通常一致的组成的3D物体。后来的系统也受限于其产生的3D物体具有通常一致的组成。
发明内容
一种使用3D打印形成组成受控的产品的计算机控制的方法，其包括将两种或更多种液体反应物组合物沉积在相应的两个或更多个储存器中；以及将所述两种或更多种液体反应物组合物混合，其又包括通过所述计算机控制所述混合的两种或更多种液体反应物组合物的质量比。所述计算机控制的方法进一步包括在所述计算机的控制下，在基底之上扫描混合液体反应物喷嘴；将所述混合液体反应物组合物沉积在所述基底上；以及在所述计算机的控制下，操作光源以使所述沉积的混合液体反应物组合物聚合。
在所述方法的一个实施方案中，所述储存器中的所述液体反应物组合物包含反应物、引发剂、致孔颗粒、加强颗粒、溶剂及其组合。在一个方面，所述反应物选自在不同的单体至聚合物的转化度下形成组成受控的共聚物的单体或单体混合物。在一个方面，所述引发剂选自用于自由基聚合、阳离子聚合或阴离子聚合的引发剂。在一个方面，所述致孔颗粒选自水溶性糖或水溶性盐和有机溶剂可溶性聚合物颗粒。在一个方面，所述加强颗粒选自金属氧化物颗粒和纳米颗粒。
在所述方法的一个实施方案中，液体反应物的质量分数由流速控制并在所述喷嘴内的容器中或在与所述喷嘴紧邻的容器中混合。在一个实施方案中，使用激光强度和照射时间控制单体至聚合物的转化度。在一个实施方案中，打印的产品经过打印后处理。在一个方面，所述打印后处理选自浸泡在水或水溶液中、浸泡在有机溶剂中和退火。
在一个实施方案中，所述方法可用于制造用于牙科修复材料、义齿、正畸治疗、牙科植入物、植入物、组织再生和组织工程的牙科装置。
在一个实施方案中，所述方法可用于制造具有包括折射率、透射率、反射率、颜色、偏振和光泽度的空间受控光学性质的光学装置。
附图说明
详细描述参考以下附图，其中相同的数字表示相同的物体，并且其中：
图1示出了用于组成受控的共聚物的3D打印的示例性系统；以及；
图2A和图2B示出了由图1的系统打印的示例性3D产品。
具体实施方式
本文公开了一种新颖的且非显而易见的3D打印系统以及相应的可用于控制物体的每个3D位置处的化学、物理和机械性质的方法或过程。在一个实施方案中，3D打印方法包括制备反应物混合物的步骤、通过扫描喷嘴挤出混合物的步骤和通过光聚合固化混合物的步骤。可以通过混合由单独的储存器供应的两种或更多种不同的反应物液体来制备混合物。混合物中每种反应物液体的相对组成可以用安装在其储存器与混合单元之间的流动控制单元控制。可以通过具有或不具有单独流动控制器的扫描喷嘴将组成受控的反应物混合物挤出到基底上。在一个实施方案中，随着混合物接触基底，用可见光或UV光照射通过光聚合快速固化混合物。
使用这种3D打印方法，可以通过各种手段控制打印的产品的化学、物理、机械和生物性质，这些手段包括但不限于：(1)混合物中反应物的相对组成；(2)混合液的流速；(3)光聚合的光的强度、照射时间和波长；以及(4)扫描喷嘴速度。可以增加额外的打印后过程(例如用于可浸出反应物去除的光退火或热退火)以改善最终产品性质。
本文公开的用于组成受控的共聚物的3D打印的方法使单个打印过程可以产生具有复杂几何形状的3D产品并连续或离散地控制该3D产品内的化学、物理和机械性质。该方法还允许将固体分散体组分添加到液体混合物中以供特定应用，例如用于牙科材料的填料纳米颗粒。反应物的光聚合3D产品可以是耐用的且生物相容的树脂网络和复合物。
图1示出了组成受控的3D打印系统的实施例。在图1中，组成受控的3D打印系统100包括液体组合物子系统、液体流动控制子系统、聚合子系统和处理器子系统。上述子系统协作以产生3D的组成受控的产品200。更具体地，系统100包括可以执行机器指令以控制系统100的特定组件的计算机110，具体地，特定组件有流动控制系统112、光照系统114和扫描台130。流动控制系统112操作阀门122i以控制反应物组合物从储存器120i流入排放组件124，并进一步操作混合室和混合阀126以控制混合的反应物组合物通过喷嘴128的沉积速率。喷嘴128将混合的反应物组合物沉积在扫描台130上。计算机110进一步控制喷嘴128在置于扫描台130上或与扫描台130成一体的基底上的三维运动。或者，喷嘴128可以是固定的，而扫描台130可以是移动的。计算机110还进一步控制可提供光(例如，激光)以固化沉积的混合反应物组合物的光照系统114。由光照系统114提供的光可以穿过透镜组件114。当打印3D产品时，可以以逐步的方式施加光。
图2A和图2B分别示出了3D打印的产品210和220。产品210是示例性的具有不同组成的3D打印的牙齿，该不同组成包括与实际人牙齿中一样的层212、214和216。产品220是根据本文公开的概念打印的具有梯度折射率(GRIN)光学性质的无像差单透镜，并且可以与常规形成的透镜20进行比较。参见本公开内容的实施例16。
使用示例性系统100，可以在3D打印期间控制液体反应物混合物的组成。此外，如以下实例中所述，示例性系统100允许通过改变混合物中反应物的相对组成以及通过其他手段来限定3D产品中所有位置的化学、机械和生物性质。此外，通过向反应物中添加额外的固体组分，如牙科产品的填料，可以进一步优化3D产品的化学、物理、机械和形态性质。进一步地，还可以通过改变具有不同流变特性的反应物的组成来调节3D产品的空间分辨率。
在一个实施方案中，储存器120i中的液体反应物组合物包含反应物、引发剂、致孔颗粒、加强颗粒、溶剂及其组合。在一个方面，反应物可以是在不同的单体至聚合物转化度下形成组成受控的共聚物的单体或单体混合物。在一个方面，引发剂可以是用于自由基聚合、阳离子聚合或阴离子聚合的引发剂。在一个方面，致孔颗粒可以是水溶性糖或水溶性盐和有机溶剂可溶性聚合物颗粒。在一个方面，加强颗粒可以是金属氧化物颗粒和纳米颗粒。
在一个实施方案中，可以操作系统100以通过控制从储存器120i的流出速率以及在喷嘴128中混合来改变液体反应物组合物的质量分数。在一个实施方案中，使用光照系统114的激光强度和照射时间控制单体至聚合物的转化度。
一旦产生了3D产品200，则可以采用额外的打印后过程(例如通过去除义齿和其他医疗装置中的可浸出反应物)以在化学、机械或生物性能方面改进最终产品。在一个实施方案中，打印的3D产品经过打印后处理。在一个方面，打印后处理包括浸泡在水或水溶液中、浸泡在有机溶剂中和退火。
在随后的实例中，发明人使用上述方法的方面来创建组成受控的3D产品并验证该3D产品的性质。过去，拉曼和红外(IR)光谱法已被用于测定光聚合反应中的乙烯基转化度。然而，常规的光谱法不足以快速监测毫秒(ms)级的反应，所述毫秒级是用于实际3D打印的关键尺度。此外，光聚合的“不可逆”性质使得不可能进行重复的同步反应监测。
为了克服当前拉曼和红外光谱方法的缺陷，可以使用灵敏的CARS光谱来监测光聚合反应。可见光用CARS信号收集物镜照亮局部区域。光照时间和周期由具有毫秒(ms)开启/关闭时间的电子快门控制。例如，可以每10ms收集CARS光谱以记录光聚合反应期间拉曼光谱的变化。
发明人还通过测定光照区域附近转换程度的空间分布来设计显微镜研究。在该研究中，在空间上测定的80μm线扫描可以每秒分辨拉曼光谱以监测来自光照区域的聚合的空间演化。这些数据将有助于发明人理解如何最好地控制3D产品的空间分辨率。
实施例1-16提供了针对发明人设想的上述公开的概念的各个实施例。
实施例1.用于组成受控的光聚合的单体混合物。
在实施例1中，使用具有自由基可聚合的乙烯基组的两个单体作为模型。实验室制备一个单体-三乙二醇-二乙烯基苄基醚(TEG-DVBE)。由于基于醚的化学结构，TEG-DVBE对水解和酯酶降解稳定。另一个单体-二甲基丙烯酸氨基甲酸酯(UDMA)是诸如用于治疗龋齿的牙科修复材料的医疗装置中的关键组分之一。商业单体UDMA由Esstech(Essington,PA,USA)提供并按原样使用。根据先前报道的程序合成TEG-DVBE并在室内对其进行完全表征。用0.2wt％的樟脑醌(CQ，Aldrich,St.Louis,MO,USA)和0.8wt％的4-N,N-二甲基氨基苯甲酸乙酯(胺，Aldrich,St’Louis,MO)激活单体混合物。
光聚合方法：将单体混合物(10μL)夹在两个Mylar薄膜之间，并使用手持式牙科固化灯(SmartLite max LED固化灯，型号：644050，Dentsply International,Milford,DE,USA)对其进行光固化。通过光与样品的距离调节光照射强度。
当将CQ/胺用作引发剂时，实施例1的单体混合物的一个独特特征是等摩尔TEG-DVBE和UDMA下的共沸组合物。共聚物中的共沸组合物意指进料单体的摩尔分数保留在聚合物中并且在整个聚合过程中恒定。考虑到UDMA的粘度(6.7Pa*s)(帕斯卡秒)比TEG-DVBE(0.028Pa*s)的粘度高约240倍，单体的粘度在聚合物链增长期间起着无关紧要的作用。
实施例2.用于组成移位光聚合的单体混合物。
与实施例1相比较，当转化度高于20％时，UDMA和三乙二醇二甲基丙烯酸酯(粘度＝0.012Pa*s)的共聚合示出显著的组成移位。在树脂网络中快速扩散的更多稀释的单体在乙烯基转化度高的情况下转化为聚合物。当混合物在聚合后玻璃化时，该组成移位是由于扩散限制。通常，低粘度单体扩散得更快并因此更有效地与活性自由基反应。因此，低粘度单体比高粘度单体更快地转化成聚合物网络。
实施例3.使用溶剂的单体混合物：增强了易处理性。
将UDMA或其他高粘度单体或单体混合物以50％的质量溶解在二氯甲烷或其他低沸点溶剂中。将UDMA溶液存储在一个容器中，准备将UDMA与其他容器的组分混合或者将UDMA单独打印出来。
实施例4.用于产生多孔结构的单体和水溶性颗粒的混合物。
在一个容器中，将单体(例如，TEGDMA)与各种质量分数的金属颗粒或金属氧化物颗粒(诸如二氧化硅、氧化铝和二氧化钛)混合。调节该混合物的粘度以流过喷嘴。准备将该容器中的混合物与其他容器的组分混合或将该混合物单独打印出来。
实施例5.单体和颗粒的混合物以提供广泛的机械性质。
在一个容器中，将单体(例如，TEGDMA)与各种质量分数的水溶性颗粒(包含糖和盐)或可通过有机溶剂溶解的聚合物颗粒(例如，聚苯乙烯颗粒)混合。调节该混合物的粘度以流过喷嘴。准备将该容器中的混合物与其他容器的组分混合或将该混合物单独打印出来。
实施例6.单体混合物的组成确定机械性质(具有不同摩尔比的相同单体对)。
通过改变UDMA和TEGDVBE的摩尔比，相应地改变3D产品的机械性质，其包括弹性模量和硬度。以使用3/1和1/1的摩尔比为例，当乙烯基转化度为80％时，3/1混合物的弹性模量(1.78+/-0.04GPa)比1/1混合物的弹性模量(1.45+/-0.04GPa)高约23％。此外，3/1混合物的硬度(14.9+/-0.8)比1/1混合物的硬度高73％。
通过3点弯曲的弯曲模量(E)和弯曲强度(F)：通过将复合材料插入不锈钢模具(25mmx2mmx2mm)并且用Mylar薄膜覆盖样品表面以防止空气抑制层来制备六个矩形样品棒，以确定弯曲模量(E)和弯曲强度(F)。使用具有钨卤素灯泡(75W及120V，43mW/cm2)的Dentsply Triad 2000可见光固化单元(Dentsply，York,PA,USA)固化样品棒。固化后，将样品棒在室温下存储24小时。使用Universal Testing Machine(Instron 5500R，InstronCorp.,Canton,MA,USA)以1mm/min的十字头速度确定样品棒的弯曲模量。将样品棒置于3点弯曲测试装置，在支持物与均匀分布的载荷之间具有20mm的距离。根据ISO4049：2009方案/方程式计算弯曲模量(E)和弯曲强度(F)值。
努氏硬度(HK)：将具有(0.25-5)N的压痕载荷的显微硬度机(Wilson Tukon 2100；Instron Corp.,Canton,MA,USA)用于HK测量(ASTM标准E384)。用于压痕的加载时间为15秒，峰值负载为15秒时停留。用10X或50X物镜测量压痕大小。通过将测试力除以压痕投影表面积来计算HK值。报告的HK值代表五次重复测量的平均值。与HK测量相关的标准不确定度为5％。
实施例7.单体混合物的组成确定机械性质(不同的单体对)。
在该实施例中，评价了UDMA/TEGDVBE和UDMA/TEGDMA的等摩尔混合物的E和HK的机械性能。含有TEGDMA的混合物的弯曲模量(E)pf(2.37+/-0.04GPa)和HK(13.6+/-1.0)分别比TEGDVBE的值高63％和48％。
实施例8.单体混合物的组成确定机械性质(使用填料)。
填料的添加显著增强了机械性质。与实施例7中含TEGDVBE的和含TEGDMA的树脂相比，具有75wt％填料的复合材料的弯曲模量(E)分别为刚性的5.6倍和4.1倍。
实施例9.通过改变通过喷嘴的液体流速控制单体混合物的组成。
在该实施例中，可以通过改变出自不同容器的液体的流速来改变单体混合物的组成。可以通过其中液体被混合的混合单元的流速来控制出自容器的液体量。
实施例10.乙烯基转化度(DC)确定机械性质。
以使用等摩尔UDMA/TEGDVBE树脂为例，当该树脂的DC从80％增加至99％时，其弯曲模量增加至70％。对于相同量的DC增加，等摩尔UDMA/TEGDMA的弯曲模量增加至41％。
使用FTIR-ATR和峰拟合方法确定乙烯基转化度(DC)。使用具有KBr分光镜、MCT/A检测器和衰减全反射(ATR)附件的Thermo Nicolet Nexus 670 FT-IR光谱仪(ThermoScientific,Madison,Wisconsin,USA)在固化后立即评价乙烯基转化度。整合TEGDVBE的乙烯基在1629cm-1处的吸收峰面积和UDMA的甲基丙烯酸酯基团在1638cm-1处的吸收峰面积，并使用1582cm-1处的TEG-DVBE的芳香族基团或1537cm-1处的UDMA的酰胺基团作为内标，计算转化度。在曲线拟合程序Fityk(版本0.9.8)的帮助下解析峰值。为了校正任何潜在的差异，通过对由NMR光谱分析的不同的树脂组成比值与通过FTIR峰拟合获得的值作图来产生标准曲线。1612cm-1处的苯基吸光度是TEG-DVBE均聚物的内标。根据下式计算乙烯基转化度(DC)：DC＝(A1/A0-A1’/A0’)/(A1/A0)100％，其中A1/A0和A1’/A0’分别代表聚合前后感兴趣的乙烯基和内标的峰面积比。感兴趣的乙烯基可以是来自TEG-DVBE、UDMA或两者的乙烯基。
实施例11.通过光强度和照射时间控制乙烯基转化度(DC)。
实时拉曼显微光谱进一步证实了UDMA/TEGDVBE的等摩尔组合物在光聚合期间随时间恒定，并且与通过光强度和照射时间控制的聚合速率无关。为了实现逐步聚合，将样品暴露于4mW/cm2的光下5秒，直至共有四次曝光。经典的最小二乘法(CLS)用于纯单体光谱，以使用TEG-DVBE和UDMA的C＝C拉伸带估计样品中未聚合的单体组成。对于预聚合的单体混合物，将每个样品的CLS评分标准化为100。随着乙烯基转化为聚合物，相关的C＝C带强度降低，并且乙烯基转化度(DC)相应地增加。在每次光照射时，该强度立即下降，然后在下一次照射之前以非常慢的速率降低。在该组实验的全时间范围(10min)内，DC达到约20％，并且TEG-DVBE/UDMA的比率始终是1/1。当样品以150mW/cm2照射20秒时，发生更快的光聚合。光照射后，该样品的DC立即达到约55％。在该DC下，树脂被固化。光强度为1000mW/cm2时，DC在几秒内达到90％。在该组实验期间，TEG-DVBE和UDMA的比例始终是1/1。
实施例12.共聚物的化学组成确定折射率。
UDMA/TEGDVBE混合物的折射率与单体的摩尔分数线性相关：y＝0.6x+1.510(R2＝0.996)，其中y是混合物的折射率，x是TEGDVBE的摩尔分数。UDMA、TEGDVBE和这两者的等摩尔混合物的折射率分别为1.510、1.571和1.528。
折射率(n)：通过在22℃下与折射率液体(n的间隔＝0.004，Cargille Labs Inc.,NJ,USA)匹配来测量共聚物及其相应的复合物的n。当样品与n-液体难以区分时，匹配的n的值基于OLYMPUS BX50光学显微镜(OLYMPUS,Tokyo,Japan)观察。
实施例13.具有不同化学组成的3D物体。
化学组成被定义为固化共聚物的组成和固化共聚物的乙烯基转化度。可以通过改变来自不同容器的液体的流速、照射强度和持续时间以及光固化后过程来改变化学组成。
实施例14.通过退火进行固化后处理。
光固化后，可以使3D产品经历基于树脂网络的玻璃化转变温度的不同温度下的退火。该退火过程在树脂网络内产生轻微移动，并因此微调3D几何形状和机械性质，如上述实施例所述。
实施例15.具有多孔结构-固化后溶解填料的3D产品。
使用激活的TEGDMA(使用引发剂CQ/胺)在一个容器中制备3D产品，并且在第二容器中将TEGDMA与筛分的NaCl晶体混合。将多孔区域中NaCl的质量分数设置在60％至84％之间，以获得最佳孔隙率和强度。在打印出产品并将其固化后，将该3D产品在去离子水中浸泡5天，多次更换水以溶解盐致孔剂，然后将其风干。成功去除NaCl颗粒。3D产品的孔径与NaCl颗粒的大小相匹配。3D产品的孔隙率与添加的NaCl的质量分数相当一致。
实施例16.3D程序化的梯度折射率(GRIN)光学元件。
梯度折射率(GRIN)光学元件是一类具有逐渐变化的材料折射率的光学元件。这样的变化用于制造具有平坦表面的透镜或没有像差的球面透镜。与非球面透镜相比，球面透镜的制造成本低廉。然而，由于固有的球面像差，球面透镜不能单独用于高性能光学仪器。可以使用非球面透镜或复合透镜(具有不同曲率和折射率的多个透镜)作为替代。然而，这些复合透镜的制造成本远高于单个球面透镜，并且复合透镜具有其他不需要的光学限制，如有限的数值孔径、整体光学厚度和减少的透射。GRIN透镜可以减小单个球面透镜或甚至具有平坦几何形状的透镜的球面像差。可重复控制常规GRIN透镜的光学性质是非常具有挑战性的。最近基于双光子聚合的技术可以制造3D光刻控制的GRIN光学元件。然而，其基于交联的折射率控制在折射率变化范围内(例如，Δn＝0.01)和由于未反应单体的缓慢转化而在长期产品稳定性方面受到限制。通过使用本文公开的概念制造的GRIN光学元件具有更宽的折射率变化范围(例如，Δn＝0.06，来自实施例12)并且通过控制完全转化组合物的比率具有更长的性能稳定性。除了GRIN光学元件的折射率之外，通过使用本文公开的概念制造的3D程序化的光学元件可以具有精确控制的其他光学性质，其包括透射率、反射率、颜色和光泽度。取决于预期的光学性质，空间控制可以是径向的、球形的、线性的或轴向的。
本文公开的方法可以实现为处理器对存储在一个或多个计算机可读取存储设备上的数据或对从其他来源接收的数据执行的操作。计算机程序(也称为程序、模块、引擎、软件、软件应用程序、脚本或代码)可以以任何形式的编程语言编写，该编程语言包含编译的或解释的语言、声明性或过程性语言，并且可以以任何形式部署，该形式包含作为独立程序或作为模块、组件、子例程、对象或其他适合在计算环境中使用的单元。计算机程序可以但不必对应于文件系统中的文件。程序可以存储在保存其他程序或数据(例如，存储在标记语言文档中的一个或多个脚本)的文件的一部分中、存储在专用于所讨论程序的单个文件中或存储在多个协调文件(例如，存储一个或多个模块、子程序或代码部分的文件)中。可以部署计算机程序以在一个计算机上或在位于一个站点或分布在多个站点并通过通信网络互连的多个计算机上执行。

Claims (15)

1.一种使用3D打印形成组成受控的产品的计算机控制的方法，其包括：
将两种或更多种液体反应物组合物沉积在相应的两个或更多个储存器中；
将所述两种或更多种液体反应物组合物混合，所述混合包括通过所述计算机控制所述混合的两种或更多种液体反应物组合物的质量比；
在所述计算机的控制下，在基底之上扫描混合液体反应物喷嘴；
将所述混合液体反应物组合物沉积在所述基底上；以及
在所述计算机的控制下，操作光源以使所述沉积的混合液体反应物组合物聚合。
2.根据权利要求1所述的方法，其中所述储存器中的所述液体反应物组合物包含反应物、引发剂、致孔颗粒、加强颗粒、溶剂及其组合。
3.根据权利要求2中的物质组合物，其中所述反应物选自在不同的单体至聚合物的转化度下形成组成受控的共聚物的单体或单体混合物。
4.根据权利要求2中的物质组合物，其中所述引发剂选自用于自由基聚合、阳离子聚合或阴离子聚合的引发剂。
5.根据权利要求2中的物质组合物，其中所述致孔颗粒选自水溶性糖或水溶性盐和有机溶剂可溶性聚合物颗粒。
6.根据权利要求2中的物质组合物，其中所述加强颗粒选自金属氧化物颗粒和纳米颗粒。
7.根据权利要求1所述的方法，其中液体反应物的质量分数由流速控制并在所述喷嘴内的容器中或在与所述喷嘴紧邻的容器中混合。
8.根据权利要求1所述的方法，其中使用激光强度和照射时间控制单体至聚合物的转化度。
9.根据权利要求1所述的方法，其包括使打印的产品经过打印后处理，其中所述打印后处理选自浸泡在水或水溶液中、浸泡在有机溶剂中和退火。
10.一种用于3D物体的组成受控的打印的方法，其包括：
将多种不同的液体反应物组合物中的每一个沉积在多个储存器中的相应储存器中；
通过计算机控制所述不同液体反应物组合物从所述储存器流入混合装置，其包括：
通过所述计算机控制所述混合装置中每种所述不同液体反应物组合物的组成百分比，所述控制包括单独调节出自所述多个储存器的相应每个储存器的流动；
均匀混合所述混合装置中的所述不同液体反应物组合物；以及
通过所述计算机，通过所述均匀混合的液体反应物组合物的多个逐步沉积和聚合来控制3D打印物体的机械性质，其包括：
在所述计算机的控制下，使用扫描喷嘴将可变量的所述均匀混合的液体反应物组合物沉积在基底上，所述计算机的控制包括控制出自所述混合装置的流动，以及
在所述计算机的控制下，使用光源聚合所沉积的可变量的所述均匀混合的液体反应物组合物。
11.根据权利要求10所述的方法，其中通过所述计算机控制组合物百分比包括控制所述混合装置中的每种不同液体反应物的重量百分比、体积百分比和摩尔比百分比中的一个或多个。
12.根据权利要求10所述的方法，其中所述液体反应物组合物形成共沸组合物，并且其中控制所述3D打印物体的机械性质包括单独调节出自所述相应储存器的流动以实现所述混合装置中的所述不同液体反应物的所需摩尔比。
13.根据权利要求10所述的方法，其中控制所述3D打印物体的机械性质包括在一个或多个所述逐步沉积和聚合期间调节所述可变量。
14.根据权利要求10所述的方法，其中控制所述3D打印物体的机械性质包括在一个或多个所述逐步沉积和聚合期间调节所述光源的强度和持续时间。
15.根据权利要求10所述的方法，其包括：
将可溶解的填料沉积在一种或多种所述不同液体反应物组合物中；
固化所述打印的3D物体；以及
溶解所述可溶解的填料以在所述打印的3D物体中产生孔隙。
CN201780059439.3A 2016-09-28 2017-09-14 组成受控的共聚物的3d打印 Pending CN109789693A (zh)

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