CN1950052B - 用官能基团均匀涂覆的粉末颗粒及其制备方法和应用 - Google Patents

用官能基团均匀涂覆的粉末颗粒及其制备方法和应用 Download PDF

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CN1950052B
CN1950052B CN2005800145705A CN200580014570A CN1950052B CN 1950052 B CN1950052 B CN 1950052B CN 2005800145705 A CN2005800145705 A CN 2005800145705A CN 200580014570 A CN200580014570 A CN 200580014570A CN 1950052 B CN1950052 B CN 1950052B
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J·贝辛杰
A·斯坦伯格
C·齐默勒
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Abstract

本发明涉及一种制备均匀涂覆有官能基团的粉末颗粒的方法，其中使原料粉末颗粒悬浮物与含至少一种官能基团的涂覆试剂相反应。该悬浮物在搅动研磨机中经均质化，并在其中使颗粒与涂覆试剂发生反应。所得的粉末在牙科材料、化妆组合物、药物组合物、粉末漆、涂料、敷层、橡胶混合物和粘合剂中适合作为填料应用。

Description

用官能基团均匀涂覆的粉末颗粒及其制备方法和应用
本发明涉及一种用于制备均匀涂覆有官能基团的粉末颗粒，特别是玻璃粉末、玻璃陶瓷粉末和/或陶瓷粉末的方法及由该方法制备的粉末和其应用。
这类粉末在大量技术领域获得广泛应用，并通过涂覆原料粉末而得到，例如这种粉末作为玻璃粉末特别是在牙科技术中用于制备化妆和药物制剂中的经充填的塑料树脂。此外，其还在外部和内部用于颜料、漆、灰泥和木材防护剂以及作为填料用于粘附剂中以提高硬度或减少膨胀。如在US-A 6010085中特别是描述了具有小粒度和最小粒度的细粒粉末的制备。此外，从US-A 5340776中已知平均粒度d50为0.2-10μm的最细的无沾污(高纯)玻璃粉末的制备，其中d50值为0.2μm意指所有颗粒的50％小于0.2μm。在此方法中将最大粒度≤300μm的玻璃粉末在搅动磨机或碾磨机中用玻璃研磨件磨碎，该研磨件的磨损不影响所得玻璃粉末的特性如折射率。在该研磨过程中，在研磨液体存在下研磨到所需粒度，之后冷冻研磨浆液，并接着通过冷冻干燥从研磨浆液中去除研磨液体。
如果将这种粉末作用牙科技术中的塑料的填料，则重要的是该玻璃粉末的折射率要与塑料折射率非常好地相一致，以达到该充填塑料的高度透明性和半透明性。但如果该玻璃粉末含杂质颗粒如来自有不同折射率的研磨机的磨损杂质，则充填塑料的透明性和半透明性以及颜色会变差，以致经常不能再应用或仅能非常有限地应用。
为此，在US-A 6010085和US-A 5340776中提及，将所有受磨损的部件如研磨容器以及研磨工件或搅动工件均涂以相同的、组成粉末的材料或涂有可用萃取、蒸馏或高温热解易于去除的塑料涂层。为在用作塑料填料时获得玻璃粉末与塑料基体的较好结合，玻璃粉末颗粒的表面通常/经常涂以合适的硅烷。这种方法例如描述于PCT/US92/04553中。该硅烷化通常可如此进行，即首先用合适的溶剂溶解硅烷并进行预水解，接着例如在混合器如在行星式混合器或在振动研磨器或圆筒研磨器中将其涂覆到已完成研磨的玻璃粉上。但在该程序中，硅烷很快形成二聚物、三聚物或还有低聚物，它们不仅形成硅烷醇附聚物，而且还与已部分涂覆的颗粒上保留的硅烷醇基形成大小达100-300μm的聚集体。用上述的混合器或研磨机不能防止这种附聚物或聚集体的形成。附聚物的其后研磨也不能产生可使用的产品。
本发明的目的在于提供一种方法，其适于均匀地官能化涂覆粉末，同时不会形成附聚物或涂覆剂粉末颗粒不会相互粘附(所谓的化学附聚)。
此外，本发明的目的是提高用现有技术方法可达到的涂覆密度。
该目的是由权利要求1所述的方法实现的。即发现，由该方法可得到高纯的无附聚的和均匀涂覆的粉末。
本发明的方法优选在悬浮剂中的粉末悬浮物中进行。原则上涂覆剂也可用作悬浮剂。但按本发明方法优选使用液态悬浮剂。可使用无机溶剂也可使用有机溶剂作为液态悬浮剂，如水或亲水性、疏水性、质子性或非质子性有机溶剂。有机溶剂中优选醇或酮。但原则上由本领域技术人员依所用粉末和/或涂覆试剂选用悬浮剂。
在本发明方法中使用的涂覆试剂具有至少一个官能基，该官能基与粉末原料可形成化学键和/或牢固吸附结合在粉末颗粒表面上。这类基团与各所用粉末材料有关。但优选应用硅烷醇基。优选的硅烷醇是烷氧基硅烷，特别是三烷氧基硅烷如3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-氯丙基三甲氧基硅烷、3-氯丙基三乙氧基硅烷、2-氨基乙基-3-氨基丙基-三甲氧基硅烷、3-缩水甘油基氧丙基三甲氧基硅烷、3-缩水甘油基氧丙基三乙氧基硅烷、十六烷基三甲氧基硅烷、异丁基三甲氧基硅烷、异丁基三乙氧基硅烷、3-巯基丙基三甲氧基硅烷、3-甲基丙烯酰氧丙基三甲氧基硅烷、3-甲基丙烯酰氧丙基三乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、辛基三甲氧基硅烷、辛基三乙氧基硅烷、戊基三甲氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷、(2-氨基乙基)-2-氨基乙基-3-氨基-丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、四甲氧基硅烷、四乙氧基硅烷。
涂覆试剂优选具有另一官能基团，该基团在涂覆后用于与相应的配体起反应。这类官能基团例如是氨基、巯基、丙烯酰基或甲基丙烯酰基、乙烯基、取代的羧基、烷基，特别是C1-C20烷基，烷氧基，特别是C1-C20烷氧基，其中烷基和烷氧基可为直链、支链、环状、杂环状和/或芳族，需要时带有双键，氰基、异氰基、氰氧基、异氰氧基、酸酐，特别是环状酸酐如琥珀酸酐，环氧基，如特别是乙氧基如缩水甘油基氧基、氨基甲酸酯基等。这类反应配体赋予粉末表面以所需特性如便于进入塑料基体、亲水或疏水特性、UV吸收、排斥污物特性、改进的可悬浮性等。
本发明方法中可应用无机和有机粉末或粉末颗粒。但优选应用无机材料粉末颗粒。特别优选的粉末材料是无机氧化物材料，如SiO2、TiO2，以及玻璃、玻璃陶瓷和形成陶瓷的材料。该材料可以是晶形的、部分晶形的和无定形的。特别优选的粉末材料是玻璃、石英、玻璃陶瓷及陶瓷。优选的溶剂和/或悬浮剂是水或至少50重量％的水和至少一种分子中含1-5个C原子的水溶性含氧有机化合物的混合物。适合作为有机化合物的是醛，如甲醛、乙醛、丙醛、丁醛、戊醛；酮，如丙酮、甲基乙基酮、二乙基甲酮；酯，如乙酸乙酯、乙酸甲酯、乙酸丙酯、甲酸甲酯、乙酯、丙酯；或酸如醋酸、丙酸。一元醇、二元醇和三元醇也是适用的。例如甘油适合作为三元醇，和例如乙二醇或丙二醇适合作为二元醇。一元醇特别适用，尤其是分子中含不超过5个C原子的一元醇。水和有机化合物的混合物是优选的。特别优选是丙酮、叔丁醇、甲醇、乙醇以及正丙醇和异丙醇。用这类醇以及酮和80-99重量％的水的混合物可达到特别好的反应以及良好的均化。
优选在预反应状态中不加入所述试剂。特别是所述试剂加入前不经预溶剂化，特别是不经预水解。
在本发明方法中所用的悬浮物中的溶剂对粉末颗粒的重量比优选为0.5∶1-5∶1，尤其是1.1∶1-4∶1，更特别优选为2∶1-4∶1，其中1.8∶1-4∶1和尤其是1.9∶1-3.5∶1尤其优选。
在本发明方法中所用的颗粒优选为细粒，其大小为d50＜5μm，尤其是＜2μm是优选的。特别优选是平均粒度d50＜0.4μm和尤其是＜0.2μm。在本发明方法中所用的颗粒可在研磨机中直接研磨到所需大小或也可以所需大小加入研磨机中。如果得到相应的原始粉末，则也可用研磨机得到粒度分布为50-400nm和尤其是180-220nm的粉末。
在本发明的优选实施方案中应用经涂覆的研磨机，例如在先前提到的DE-A 4100604或US-A 6010085中所述的研磨机。本发明中优选的涂层材料是聚合树脂。优选的聚合树脂是聚氨酯。
本发明中试剂的使用量按粉末物料计为0.5-15重量％。优选的用量范围为1-12重量％，其中特别优选为2-10重量％。适于各种应用的最佳量也与粉末的所需最终细度有关，并可由本领域技术人员用简单试验而定。
反应结束后，从研磨机中取出悬浮物，并优选通过干燥去除悬浮剂以及未反应的试剂。通过加热(需要时在真空下)进行的溶剂或悬浮剂的蒸发是特别适用的干燥方法。在许多情况下优选的和也是适用的方法是冷冻干燥法。
在一些情况下，本发明中优选用合适溶剂来萃取末反应的试剂。优选的溶剂是对待去除的试剂有特别好的溶剂化作用的溶剂。在三烷基硅烷情况下，特别优选是醇。由于磨损而在反应产物中所含的塑料(如树脂，特别是聚氨酯)杂质在本发明中也可通过萃取如醚萃取而去除。
已表明，用本发明方法可得到特别细的和高纯的涂覆粉末颗粒。此外，由此可认为本反明所得的涂层是单层。再则，与现有技术方法相比，用本发明方法可大大减少未结合的硅烷量。用本发明方法可得到特别均匀涂覆的粉末颗粒，因为在涂覆过程中防止了附聚或聚集。
本发明还涉及经涂覆的粉末材料本身，特别是粒度d50＜2μm的经致密涂覆以单层的粉末材料，其中粒度＜1.5μm和特别是＜1μm是特别优选的。该粉末不含聚集体和附聚体。特别优选是粒度d50＜0.7μm和＜0.4μm的粉末。更优选是粒度＜0.2μm的粉末。D50意指平均颗粒直径，其表征穿过筛的颗粒细度，即在给定大小的筛情况下，有50％，特别是50重量％的颗粒穿过筛孔，而另50％未穿过该筛。
本发明方法如下进行：
在搅动研磨机中，先将各所需的待涂覆玻璃材料湿磨到所需大小，接着随即或在任何其后的时间点向该搅动机中混入试剂，不进行预水解。该试剂在浆液中先经均质化，在玻璃粉末浆中均匀分布后才逐渐水解。
该硅烷化反应的终点是通过粘度强烈增加表征的，以致如果该粘度不再变化或几乎不再变化，就可认为该硅烷化反应结束了。
经约1小时后，粘度明显增加。如果粘度不再变化(约再过30分钟后)则反应结束。泵出浆状物并干燥之。
硅烷含量以有机残余物经煅烧后的重量损失测定。
未牢固结合的硅烷的量如下测定：粉末经异丙醇洗涤，并接着按上述以有机残余物经煅烧后的重量损失来测定硅烷含量。
比表面积用Micromeritics公司的Flow Sorb 2300型BET仪按DIN66131(1990)的BET法测定。气体由氦和氮的70∶30混合物组成。
按要达到的最终细度，经预研磨的玻璃的粒度d50为0.9-1.2μm、0.6-0.9μm或0.2-0.6μm。粒度分布由Quantachrome公司的Cilas1064L型激光颗粒测定仪测定。测定在研磨浆状物中进行。测量精度为±1μm。
本发明还涉及用本发明方法得到的颗粒作为填料的应用，特别是在牙科材料如假牙或假牙部件以及牙充填物中的应用，在化妆品和药物制剂如软膏和糊剂以及唇膏中的增稠剂和/或防腐剂的应用，作为防护涂层和敷层如颜料、漆、灰泥和木材防护剂在内部和外部应用，特别是作为UV吸收剂或防UV辐射涂层的应用，以及在粘附剂中的应用，如用于增加硬度或用于减少收缩效应和膨胀效应以及用于防沉降。
本发明将由下列实施例进行详述。
实施例
实施例1
在本发明的一个实施方式中，将500g粒度d50＝0.7μm的超细玻璃粉末以水浆形式加到揽动研磨机(PML V+H型，DRAIS GmbH，德国)中。在该浆经足够的均质化后，将4重量％的甲基丙烯酰氧基丙基三甲氧基硅烷在3-5分钟内慢慢加到该浆中。经约1小时后，该浆的粘度明显增加。再经30分钟后完成硅烷化，并泵出浆状物。该浆经干燥后形成硅烷化的无附聚体的高纯玻璃粉末。经灼烧损失测定的硅烷含量为2.5％。未结合的硅烷含量为0％。该硅烷化的粉末的比表面积为20m2/g。如此所得的粉末的电子显微镜照片示于图1中(定标＝10μm)。
对比实施例2
在混合装置中将500g的粒度d50＝0.7μm的超细玻璃粉末与经预水解的硅烷(4重量％)混合。经约2h浸润时间后，排出该混合物并干燥。经灼烧损失测定的硅烷含量为1.8％。未结合的硅烷含量为22％。该硅烷化的粉末的比表面积为7m2/g。如此所得的粉末的电子显微镜照片示于图2中(定标＝5μm)。
实施例3
在本发明的一个实施方案中，将500g粒度d50＝1.0μm的超细玻璃粉末以水浆形式加到揽动研磨机中。在该浆经足够的均质化后，将3重量％的甲基丙烯酰氧基丙基三甲氧基硅烷慢慢加到该浆中。经约1小时后，该浆的粘度明显增加。再经30分钟后完成硅烷化，并泵出该浆状物。该浆状物经干燥后形成硅烷化的无附聚体的高纯玻璃粉末。经灼烧损失测定的硅烷含量为1.9％。未结合的硅烷含量为0％。该硅烷化的粉末的比表面积为10m2/g。如此所得的粉末的电子显微镜照片示于图3中(定标＝5μm)。
对比实施例4
在混合装置中将500g的粒度d50＝1.0μm的超细玻璃粉末与经预水解的硅烷(3重量％)混合。经约2h浸润时间后，排出该混合物并干燥。经灼烧损失测定的硅烷含量为1.5％。未结合的硅烷含量为22％。该硅烷化的粉末的比表面积为3.2m2/g。如此所得的粉末的电子显微镜照片示于图4中(定标＝5μm)。
实施例5
在本发明的一个实施方案中，在实验室揽动研磨机中将500g的粒度d50＝0.4μm的超细玻璃粉末与水一起制成浆状物并装入装置中。在该浆经足够的均质化后，将9重量％的甲基丙烯酰氧基丙基三甲氧基硅烷慢慢加到该浆中。经约1小时后，该浆的粘度明显增加。再经30分钟后完成硅烷化，并泵出该浆。该浆经干燥后形成硅烷化的无附聚体的高纯玻璃粉末。经灼烧损失测定的硅烷含量为5％。未结合的硅烷含量为0％。该硅烷化的粉末的比表面积为40m2/g。如此所得的粉末的电子显微镜照片示于图5中(定标＝10μm)。
对比实施例6
在混合装置中将500g的粒度d50＝0.4μm的超细玻璃粉末与经预水解的硅烷(9重量％)混合。经约2h浸润时间后，排出该混合物并干燥。经灼烧损失测定的硅烷含量为5％。未结合的硅烷含量为24.5％。该硅烷化的粉末的比表面积为10m2/g。如此所得的粉末的电子显微镜照片示于图6中(定标＝20μm)。

Claims (12)

1.一种在含有溶剂和原料粉末颗粒的悬浮液中制备均匀涂覆有官能基团的直径d50小于2μm的无机氧化物粉末颗粒的方法，该方法是通过使原料粉末颗粒与含至少一种能与粉末原料形成化学键和/或牢固吸附结合在所述粉末原料表面上的官能基团的涂覆试剂相反应而进行的，其特征在于，使用硅烷作为涂覆试剂，所述悬浮物在搅动研磨机中经均质化，其中使所述颗粒与涂覆试剂发生反应；所述溶剂为含有至少50重量％水和至少一种分子中含1-5个碳原子的水溶性含氧有机化合物的混合物，溶剂对粉末颗粒的重量比为0.5∶1至5∶1。
2.权利要求1的方法，其特征在于，所述颗粒由玻璃、石英和/或陶瓷组成。
3.权利要求2的方法，其特征在于，所述陶瓷为玻璃陶瓷。
4.权利要求1的方法，其特征在于，所述反应在经涂覆过的搅动研磨机中进行。
5.权利要求1-4之一的方法，其特征在于，用水性悬浮剂实现悬浮。
6.权利要求1-4之一的方法，其特征在于，制出的颗粒的比表面积为5-40m2/g。
7.权利要求1-4之一的方法，其特征在于，所述悬浮物中悬浮剂与固体颗粒的重量比为1∶1-5∶1。
8.权利要求1-4之一的方法，其特征在于，所述反应中的粉末对涂覆试剂的重量比为1∶0.005-1∶0.2。
9.按权利要求1-8之一的方法所制得的均匀涂覆的粉末。
10.权利要求9的粉末或按权利要求1-8之一所得的粉末在牙科材料、化妆组合物、药物组合物、粉末漆、涂料或橡胶混合物中作为填料的应用。
11.权利要求9的粉末或按权利要求1-8之一所得的粉末在敷层中作为填料的应用。
12.权利要求9的粉末或按权利要求1-8之一所得的粉末在粘合剂中作为填料的应用。
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GB2429705A (en) 2007-03-07
US20070184185A1 (en) 2007-08-09
US8349399B2 (en) 2013-01-08
GB2429705B (en) 2009-11-25
JP2007536416A (ja) 2007-12-13
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