CN112048192B - 一种具有两亲性的Janus有机颜料粒子的制备方法 - Google Patents
一种具有两亲性的Janus有机颜料粒子的制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有两亲性的Janus有机颜料粒子的制备方法，包括：优选有机颜料作为稳定剂，添加乳化剂，制得Pickering乳液；通过冷却固化石蜡的Pickering乳液固定有机颜料粒子，再将暴露在水中的部分有机颜料粒子进行亲水改性，而镶嵌在石蜡中的有机颜料保持原有特性；将石蜡溶解得即亲水又亲油的两亲性Janus有机颜料粒子。本发明基于有机颜料粒子稳定的Pickering乳液作为模板，对有机颜料进行单面改性，所得改性颜料粒子具有典型的Janus结构，即增加了有机颜料的表面润湿性、水相易分散性，也保留了颜料疏水的特性，提升有机颜料对聚合物涂料的着色效果。
Description
技术领域
本发明涉及精细化工领域，具体涉及一种具有两亲性的Janus有机颜料粒子的制备方法。
背景技术
近年来，具有各向异性或表面特性的粒子(Janus粒子)凭借其新颖的形貌在材料科学、生物医学、高性能生物传感器等领域造成巨大的影响。“Janus”一词最早来源于古希腊的双面罗马神“Janus”，是指具有两面不同化学或极性的化学粒子。Janus粒子最吸引人的地方是其不对称结构，由于Janus粒子中同时存在两个不同的区域，意味着其可控的自组装和表面活性，例如可以在同一粒子中设计成具有不同的疏水性。此外，Janus纳米复合材料具有均匀的尺寸、独特的表面特性、空间分离的功能和对多种刺激的响应，在化学反应催化、生物传感和药物传递等领域具有广泛的应用前景。然而，为了快速发展Janus粒子的应用，需要对其固有特性进行复杂的调控，这些特性通常取决于颗粒的形状、组成和大小以及合适的表面改性。因此如何制备各向异性的Janus粒子是一个艰巨的挑战。
一般而言，根据制备方法的不同，可以将Janus纳米粒子分为三大类。第一类Janus纳米颗粒可以通过自组装获得，例如在纳米颗粒表面表现出竞争吸附的配体混合物，还有嵌段共聚物制备Janus粒子。第二类Janus纳米颗粒的制备原理来源于两种不同物质在外部环境变化下发生相分离，这种物质通常是两种聚合物，或一种聚合物和一种无机材料，但是该方法的制备条件是在制备过程中两种物质能够发生相分离，产物粒子的形貌、结构受单个组分的影响较大。第三组制备方法主要是通过掩蔽步骤获得的Janus纳米粒子，在掩蔽步骤中，粒子被困在两相之间的界面处，因此仅需要在一侧对粒子表面进行化学或物理试剂修饰，就可以使纳米粒子具有各向异性的表面和体特性，这是最直接的方法来制备特定结构的Janus粒子。固定化过程通常是通过在界面之间捕获纳米粒子来实现的，因此这种方法实际上适用于任何形状的纳米粒子，并且提供了用多种官能团修饰纳米粒子表面的可能性。目前，通过在液/液界面之间均匀屏蔽部分的纳米粒子，然后在水相中对这些纳米粒子进行化学改性，合成Janus粒子的方法称为“Pickering乳液改性法”。使用固体粒子作为稳定剂，在两液相界面上负载固体纳米粒子，是制备尺寸和表面功能可控的Janus胶体颗粒的理想方法之一。有机和无机纳米粒子的单层膜只有在其半球表面经过化学修饰，而剩余表面受到保护时，才能稳定乳状液滴。这种方法提供了制备结构复杂的Janus粒子的可能性，被越来越多地认为是制备Janus粒子的可行方法之一。
有机颜料是一种有色、细颗粒粉状的有机化合物，广泛地用于油墨、油漆、合成纤维的原浆着色，以及织物的涂料印花、塑料及橡胶、皮革的着色等，产量占染料总产量的四分之一左右。然而有机颜料因其表面能高、粒径大、粒径分布广、遮盖力低、分散性差、稳定性差等缺点，限制了其在涂层印染中的使用。所以现在人们在使用有机颜料之前，往往先对其进行改性，来降低它的表面能，提高表面润湿性。目前，改性有机颜料的常用制备方法是对其完全封装。迄今为止，已经有很多实验制备出表面润湿性高的有机颜料微胶囊粒子。例如有研究学者使用可聚合乳化剂，预分散C.I.颜料蓝15:3，再加入共聚单体，聚合包覆有机颜料。结果表明，包覆后的复合粒子呈核-壳结构，在颜料表面形成了聚合物包覆层，聚合物包覆颜料分散体改善了颜料表面润湿性，使颜料在水中可以很好的分散[Colloids andSurfaces A:Physicochemical and Engineering Aspects 2011,384(1)]。然而，对有机颜料的完全包覆，往往导致颜料亲水有余而亲油不足，在后期与粘连剂的使用时会导致颜料的析出。为解决这一问题，公布号CN104212197A的中国专利公开了一种基于硅溶胶非连续沉积制备两亲性有机颜料的方法，通过硅溶胶非连续沉积有机颜料表面，其中无机沉积部分亲水，无沉积部分疏水，制备出即亲水又亲油的有机颜料。此外，又有研究学者以不同亲疏水性的有机颜料颗粒为稳定剂，在等油水比和固定总颗粒浓度条件下，制备了Pickering乳液[Langmuir 2018,34(17):5040-5051]。但是由于有机颜料微观呈不规则几何形状，一般方法难以制备结构规整的有机颜料Janus粒子。在此基础上，我们提出利用Pickering乳液改性法制备Janus有机颜料粒子，以Pickering乳液为模板再对颜料进行改性，使有机颜料具备亲水的同时保留疏水的特性，有利于有机颜料的在织物涂层方便的应用。
发明内容
本发明提供了一种基于Pickering乳液制备双亲性Janus有机颜料粒子的方法，首先利用有机颜料充当稳定剂制备液体石蜡分散在水相中O/W类型的Pickering乳液；然后通过亲水改性试剂包覆在部分暴露于水相中的有机颜料；最后溶解石蜡，得到具有双亲性的Janus有机颜料粒子。
一种具有两亲性的Janus有机颜料粒子的制备方法，包括以下步骤：
(1)有机颜料微细粒子稳定Pickering乳液的制备：
将有机颜料与乳化剂分散在水相中，加入固体石蜡，并升高温度加热石蜡熔化，超声乳化，获得有机颜料微细粒子稳定的Pickering乳液，再冷却至室温，固化石蜡，获得固定有机颜料粒子分散液。
升高温度至60～80℃加热石蜡熔化。
(2)两亲性Janus有机颜料粒子的制备：
将固定有机颜料粒子分散液使用氨水调节pH为8.0～10.0，加入颜料亲水改性试剂，反应，然后离心，去除上层清液后，向沉淀中加入固体石蜡的良溶剂，再离心洗涤，获得具有两亲性的Janus有机颜料粒子。
本发明进一步的改进在于，步骤(1)中，通过添加亲水乳化剂辅助有机颜料制备Pickering乳液，使Pickering乳液的稳定性提高，同时，令与水接触角不同的有机颜料均可以制备出Pickering乳液。
本发明优选有机颜料作为稳定剂，添加乳化剂，制得有机颜料稳定的石蜡O/W类型的Pickering乳液；通过冷却固化石蜡的Pickering乳液固定有机颜料粒子，再将暴露在水中的部分有机颜料粒子进行亲水改性，而镶嵌在石蜡中的有机颜料保持原有特性；将石蜡溶解得即亲水又亲油的两亲性Janus有机颜料粒子。本发明基于有机颜料粒子稳定的Pickering乳液作为模板，对有机颜料进行单面改性，所得改性颜料粒子具有典型的Janus结构，即增加了有机颜料的表面润湿性、水相易分散性，也保留了颜料疏水的特性，提升有机颜料对聚合物涂料的着色效果。
为取得更好的发明效果，对本发明进行进一步的优选：
步骤(1)中，所述的有机颜料作为Pickering乳液稳定剂,可以是与水接触角为51°～98°的有机颜料，如：Pigment Red 122、Pigment Yellow 83和Pigment Red 146。
所述的乳化剂为十二烷基硫酸钠、烷基酚聚氧乙烯醚-10、十六烷基三甲基溴化铵、烯烃氧基磺酸盐的一种或多种。
所述的乳化剂的加入量为有机颜料质量的0.1％～5％。
所述的充当Pickering乳液稳定剂的有机颜料占液体石蜡质量的0.1％～30％，即所述的液体石蜡与有机颜料的质量比100：01～30。Pickering乳液的稳定性和稳定剂的用量有关，当颜料使用质量低于20％时，如图2所示制得的乳液粒径较大，稳定性较差，当颜料使用质量高于20％时，制得的乳液粒径较小但是分布不均一。当颜料使用质量等于20％时，如图3所示制得的乳液粒径小，分布较好。
步骤(1)中，所述的有机颜料稳定的Pickering乳液油水比为1∶1.5～9。即所述的固体石蜡与水相的质量比为1∶1.5～9，最优选为1∶9。油水比不但决定Pickering乳液稳定性还决定其乳液的类型。实验发现当油相添加比例较高时，难以制备出稳定O/W类型的Pickering乳液，因此，本发明所用的油水比为1∶9。
步骤(1)中，升高温度至60～80℃加热石蜡熔化。
步骤(1)中，所述的有机颜料稳定的Pickering乳液制备时超声时间为2min～30min，功率为100W～450W。当增加超声功率和超声时间时，制得的有机颜料稳定的Pickering乳液粒径逐渐变小，但是当超声功率大于300W，超声时间高于8min时，乳液粒径变化趋于稳定。即所述的超声乳化的条件为：使用100W～450W功率超声乳化2min～30min。
所述的有机颜料稳定的Pickering乳液的粒径为50nm～1200nm。
步骤(2)中，所述的两亲性Janus有机颜料粒子改性试剂。当在碱性环境下使用3-氨丙基三乙氧基硅烷或正硅酸乙酯时，可以均匀地包覆有机颜料，改变颜料与水的接触角，增加颜料部分的亲水性，有利于颜料在水中的分散。即所述的颜料亲水改性试剂为多巴胺试剂、3-氨丙基三乙氧基硅烷试剂、正硅酸乙酯试剂、钛酸丁酯试剂、2-[甲氧基(聚乙烯氧基)丙基]三甲氧基硅烷的一种或多种。进一步优选为3-氨丙基三乙氧基硅烷或正硅酸乙酯。
步骤(2)中，所述的两亲性Janus有机颜料粒子改性试剂的用量占有机颜料质量比重为40％～110％，通过透射电镜观察改性颜料微观结构发现当改性试剂的用量占颜料质量的70％～90％时制备的有机颜料具有明显的Janus结构。即所述的颜料亲水改性试剂的加入量为有机颜料质量40％～110％。
步骤(2)中，所述的两亲性Janus有机颜料粒子使用石蜡的良溶剂溶解石蜡，再用去离子水离心洗涤三次得到具有两亲性的Janus有机颜料粒子。
步骤(2)中，所述的反应的条件为：在25℃～65℃下反应6～8h。
与现有技术相比，本发明具有如下有益效果：
一、本发明使用Pickering乳液改性法制备Janus有机颜料粒子，使有机颜料同时具备亲水/疏水两种特性，不但增加了颜料表面的润湿性，还保留了颜料对聚合物的相容性，使颜料在聚合物胶膜中也能良好分散。
二、本发明制备的改性有机颜料相较于以往对有机颜料的完全包覆不同，减少了包覆层对光的散射效应，同时对基底具有遮盖作用，增加了有机颜料的着色效果，使涂层的色彩更加鲜艳。
三、本发明改性的颜料不但具有良好的分散性，而且其耐热、耐候性也有所提升(如图4数据所示)。
附图说明
图1是不同的有机颜料亲水改性试剂的结构式，其中，TEOS为正硅酸乙酯，ATPES为3-氨丙基三乙氧基硅烷，TBOT为钛酸丁酯，PETOMS为2-[甲氧基(聚乙烯氧基)丙基]三甲氧基硅烷。
图2是对比例1中制备的有机颜料微细粒子稳定Pickering乳液的光学显微镜图。
图3是实施例4中制备的有机颜料微细粒子稳定Pickering乳液的光学显微镜图。
图4是实施例4中制备的Janus有机颜料粒子和原始颜料的热重分析对比图。
图5是实施例1中制备的Janus有机颜料粒子的制备方法机理图。
具体实施方式
下面结合对比例1以及实施例1～13对本发明进行进一步描述，步骤如下：
如图5所示，按照表1所述的有机颜料水分散液A为原料，加入乳化剂，搅拌15min后，加入如表1比例的固体石蜡，加热溶液直至70℃石蜡熔化。然后使用超声波细胞粉碎机在300W功率超声乳化8min，得到有机颜料微细粒子稳定的Pickering乳液。
将Pickering乳液冷却至室温25℃，固化石蜡，再采用1500rpm的速率进行离心，去除上清液后，获得固定有机颜料粒子分散液B。
按照表2的配方，将固定有机颜料粒子分散液B使用氨水调节pH为8.0～10.0，然后加入如表2所示质量的亲水改性试剂(3-氨丙基三乙氧基硅烷)，在25℃～65℃下搅拌反应7h，然后采用1500rpm的速率进行离心，保留沉淀物C。
向沉淀物C中加入石蜡的良溶剂溶解固体石蜡，使用去离子水离心洗涤三次，获得具有两亲性的Janus有机颜料粒子。
表1：不同原料比例制备的有机颜料Pickering乳液的配方
表2：制备Janus有机颜料粒子的配方
通过激光粒度仪(日本Holiba公司的LB-550)测量有机颜料微细粒子稳定的Pickering乳液的粒径分布并得到其平均粒径值；通过德国KRUSS PSA100接触角测试仪来测试改性颜料的水、油接触角。
经过观察实例1～13得到一种具有双亲性的有机颜料Janus粒子。对比例1制备的有机颜料稳定的Pickering乳液的光学显微镜图如图2所示。经过对比实例4制备的有机颜料稳定的Pickering乳液的光学显微镜图如图3所示。
如图4数据所示，本发明改性的颜料不但具有良好的分散性，而且其耐热、耐候性也有所提升。
Claims (9)
1.一种具有两亲性的Janus有机颜料粒子的制备方法，其特征在于，包括以下步骤：
(1)将有机颜料与乳化剂分散在水相中，加入固体石蜡，并升高温度加热石蜡熔化，超声乳化，获得有机颜料微细粒子稳定的Pickering乳液，再冷却，固化石蜡，获得固定有机颜料粒子分散液；
(2)将固定有机颜料粒子分散液使用氨水调节pH为8.0～10.0，加入颜料亲水改性试剂，反应，然后离心，去除上层清液后，向沉淀中加入固体石蜡的良溶剂，再离心洗涤，获得具有两亲性的Janus有机颜料粒子。
2.根据权利要求1所述的具有两亲性的Janus有机颜料粒子的制备方法，其特征在于，步骤(1)中，所述的有机颜料为与水接触角为51°～98°的有机颜料。
3.根据权利要求1所述的具有两亲性的Janus有机颜料粒子的制备方法，其特征在于，步骤(1)中，所述的乳化剂为十二烷基硫酸钠、烷基酚聚氧乙烯醚-10、十六烷基三甲基溴化铵、烯烃氧基磺酸盐的一种或多种。
4.根据权利要求1所述的具有两亲性的Janus有机颜料粒子的制备方法，其特征在于，步骤(1)中，所述的乳化剂的加入量为有机颜料质量的0.1％～5％。
5.根据权利要求1所述的具有两亲性的Janus有机颜料粒子的制备方法，其特征在于，步骤(1)中，所述的固体石蜡与水相的质量比为1∶1.5～9。
6.根据权利要求1所述的具有两亲性的Janus有机颜料粒子的制备方法，其特征在于，步骤(1)中，升高温度至60～80℃加热石蜡熔化；
所述的超声乳化的条件为：使用100W～450W功率超声乳化2min～30min。
7.根据权利要求1所述的具有两亲性的Janus有机颜料粒子的制备方法，其特征在于，步骤(2)中，所述的颜料亲水改性试剂为多巴胺、3-氨丙基三乙氧基硅烷、正硅酸乙酯、钛酸丁酯、2-[甲氧基(聚乙烯氧基)丙基]三甲氧基硅烷中的一种或多种。
8.根据权利要求1所述的具有两亲性的Janus有机颜料粒子的制备方法，其特征在于，步骤(2)中，所述的颜料亲水改性试剂的加入量为有机颜料质量40％～110％。
9.根据权利要求1所述的具有两亲性的Janus有机颜料粒子的制备方法，其特征在于，步骤(2)中，所述的反应的条件为：在25℃～65℃下反应6～8h。
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