CN111440352A - 磁性聚合物微球及其制备方法 - Google Patents

磁性聚合物微球及其制备方法 Download PDF

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CN111440352A
CN111440352A CN202010296114.0A CN202010296114A CN111440352A CN 111440352 A CN111440352 A CN 111440352A CN 202010296114 A CN202010296114 A CN 202010296114A CN 111440352 A CN111440352 A CN 111440352A
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cationic dye
inorganic nanoparticles
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于晓平
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TCL China Star Optoelectronics Technology Co Ltd
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Abstract

本申请提供一种阳离子染料吸附剂，所述阳离子染料吸附剂包括中空聚合物微球，所述中空聚合物微球表面分散有磺酸基，所述中空聚合物微球的材料选自由下式(1)至(3)所表示的化合物中的一个或多个，
Figure DDA0002452253080000011
Figure DDA0002452253080000021
其中，n1、n2、n3为大于或者等于0的整数，在式(1)至(3)所表示的化合物中，环上的氢原子被取代基取代或者不被取代。

Description

磁性聚合物微球及其制备方法
技术领域
本申请涉及材料制备领域，尤其涉及一种磁性聚合物微球及其制备方法。
背景技术
彩色滤光片(Color filter，CF)是液晶显示器(Liquid Crystal Display，LCD)实现彩色化的关键部件。彩色滤光片的工作原理是通过过滤背光产生红(R)，绿(G)，蓝(B)三原色的光线，再使三原色的光线以不同的比例混合而得到各种色彩的光，从而使LCD显现彩色。彩色滤光片的色纯度/辉度/对比度等性能会直接影响到LCD的色彩饱和度、显示亮度及对比度等性能。为了提升LCD的色彩饱和度、显示亮度及对比度等性能，近年来染料(dye)逐渐被应用到彩色滤光片中，具有加入了染料的彩色滤光片的液晶显示器在高色域、高亮度和高对比度等方面有着优异的表现。由于染料属于小分子化合物，溶解在水中形成有色水，如何去除废水中的染料成为LCD行业亟需解决的问题。
发明内容
有鉴于此，本申请目的在于提供一种能够有效去除废水中的染料的磁性聚合物微球及其制备方法。
本申请提供一种阳离子染料吸附剂，所述阳离子染料吸附剂包括中空聚合物微球，所述中空聚合物微球表面分散有磺酸基，所述中空聚合物微球的材料选自由下式(1)至(3)所表示的化合物中的一个或多个，
Figure BDA0002452253060000011
Figure BDA0002452253060000021
其中，n1、n2、n3为大于或者等于0的整数，在式(1)至(3)所表示的化合物中，环上的氢原子被取代基取代或者不被取代。
在一种实施方式中，所述中空聚合物微球的分子式如下式(4)至(6)的任一项所示：
Figure BDA0002452253060000031
Figure BDA0002452253060000041
其中，m1至m16为大于或者等于0的整数，且m1至m4不同时为0，m5至m12不同时为0，m13至m16不同时为0。
在一种实施方式中，所述磺酸基的浓度为1.5mmol/g至3.0mmol/g。
在一种实施方式中，所述中空聚合物微球的厚度为10nm至100nm。
在一种实施方式中，所述中空聚合物微球的内径位于50nm至1000nm的范围内。
本申请还提供一种阳离子染料吸附剂的制备方法，其包括以下步骤：
将无机纳米粒子，单体以及催化剂分散于溶液中，在氩气氛围下加热反应，在所述无机纳米粒子表面形成一层聚合物，其中，所述单体选自由下式(7)至(9)所表示的化合物中的一个或多个，
Figure BDA0002452253060000051
在式(7)至(9)所表示的化合物中，环上的氢原子被取代基取代或者不被取代；
除去所述无机纳米粒子以形成中空聚合物微球；
对所述中空聚合物微球表面进行磺化处理，形成具有磺酸基的中空聚合物微球，获得所述阳离子染料吸附剂。
在一种实施方式中，所述无机纳米粒子材料的摩尔量与所述单体的摩尔量的比例为200:1至10:1。
在一种实施方式中，在所述无机纳米粒子表面形成一层聚合物的步骤中，反应温度为50℃至70℃，反应时间为24h-48h。
在一种实施方式中，所述无机纳米粒子的粒径位于50nm到1000nm的范围内。
在一种实施方式中，所述无机纳米粒子选自氧化铝、氧化锌、氧化钙、氧化镁的一种或多种。
相较于现有技术，本申请所提供的阳离子染料吸附剂由于中空的聚合物微球经过磺化处理，聚合物微球的表面含有丰富的磺酸基，在溶液中呈现负电性状态，通过静电吸附作用力，能够有效地高选择性地吸附阳离子染料。同时，中空的结构可以为聚合物微球提供更高的比表面积，相较于实心的聚合物微球具有更高的吸附力。
附图说明
为了更清楚地说明本申请中的技术方案，下面将对实施方式描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施方式，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本申请第一实施方式提供的阳离子染料吸附剂的示意图。
图2是本申请第二实施方式提供的阳离子染料吸附剂的制备方法的示意图。
图3的(A)为本申请第二实施方式的表面包裹有聚合物外壳的无机纳米粒子的电子显微镜照片，图3的(B)为本申请第二实施方式的中空聚合物微球的电子显微镜照片。
图4为分别使用本申请所提供的三种阳离子染料吸附剂吸附罗丹明染料的移除率的对比图。
具体实施方式
下面将结合本申请实施方式中的附图，对本申请中的技术方案进行清楚、完整地描述。显然，所描述的实施方式仅仅是本申请一部分实施方式，而不是全部的实施方式。基于本申请中的实施方式，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本申请保护的范围。
请参考图1，本申请第一实施方式提供一种阳离子染料吸附剂，其可用于吸附水中的污染物，例如用于吸附LCD的滤光片制程中产生的废水中所含的染料。
阳离子染料吸附剂包括中空聚合物微球100，中空聚合物微球表面分散有磺酸基。中空聚合物微球100的材料选自由下式(1)至(3)所表示的化合物中的一个或多个，
Figure BDA0002452253060000071
Figure BDA0002452253060000081
其中，n1、n2、n3为大于或者等于0的整数，在式(1)至(3)所表示的化合物中，环(包括苯环和氮杂环)上的氢原子可以被取代基取代，也可以不被取代。取代基可以是卤素原子、烷基、烷氧基、羟基、羧基、铵基等。在一个实施方式中，取代基为碳原子数小于或者等于6的基团。
在本申请中，磺酸基仅分布在中空聚合物微球的表面。也就是说，中空聚合物微球表面的材料上连接有磺酸基，除中空聚合物微球表面以外的材料没有连接磺酸基。
表面分散有磺酸基的中空聚合物微球的分子式如下式(4)至(6)的任一项所示：
Figure BDA0002452253060000091
Figure BDA0002452253060000101
其中，m1至m16为大于或者等于0的整数，且m1至m4不同时为0，m5至m12不同时为0，m13至m16不同时为0。
在本申请提供的阳离子染料吸附剂中，磺酸基的浓度为1.5mmol/g至3.0mmol/g。当磺酸基的浓度在这个范围内时，阳离子染料吸附剂的吸附效果最佳。
中空聚合物微球的厚度为10nm至100nm。中空聚合物微球的内径位于50nm至1000nm的范围内。
请参考图2，本申请还提供一种阳离子染料吸附剂的制备方法，其包括以下步骤：
S1：将无机纳米粒子，单体以及催化剂分散于溶液中，在氩气氛围下加热反应，在无机纳米粒子表面形成一层聚合物，其中，单体选自由下式(7)至(9)所表示的化合物中的一个或多个。
Figure BDA0002452253060000111
在式(7)至(9)所表示的化合物中，环(包括苯环和氮杂环)上的氢原子可以被取代基取代，也可以不被取代。取代基可以是卤素原子、烷基、烷氧基、羟基、羧基、铵基等。在一个实施方式中，取代基为碳原子数小于或者等于6的基团。
在此步骤中，无机纳米粒子材料的摩尔量与单体的摩尔量的比例为200:1至10:1。例如，当采用的无机纳米粒子为氧化锌时，用于形成无机纳米粒子的氧化锌的摩尔量与单体的摩尔量比为200:1至10:1。催化剂可以为AlCl3。反应温度为50℃至70℃，反应时间为24h-48h。本申请不限定无机纳米粒子的种类。任何可以被酸或者碱腐蚀的无机纳米粒子均可用于本申请。在一个实施方式中，无机纳米粒子选自氧化铝、氧化锌、氧化钙、氧化镁的一种或多种。无机纳米粒子的粒径位于50nm到1000nm的范围内。
S2：除去无机纳米粒子以形成中空聚合物微球。在此步骤中，利用酸或者碱腐蚀除去无机纳米粒子。中空聚合物微球的厚度为10nm至100nm。
S3：对聚合物微球表面进行磺化处理，形成具有磺酸基的中空聚合物微球，获得阳离子染料吸附剂。磺酸基的浓度为1.5mmol/g至3.0mmol/g。磺化处理可以通过将中空聚合物微球放入发烟硫酸中，加热至90℃至120℃，反应12h进行。
下面说明本申请提供的阳离子吸附剂的制备方法的一个具体实施例。
将6mmol氧化锌纳米球与0.6mmol式(7)所表示的单体混合，加入200ml CHCl3中超声1h，去除溶剂后与AlCl3一起加入反应釜中，在氩气氛围下60℃反应42h，然后提纯备用。请参考图3的(A)，图3的(A)为该步骤中制备出的表面包裹有聚合物外壳的无机纳米粒子的电子显微镜照片。
将制备的纳米粒子加入到3mol/L的HCl溶液中，搅拌20min，离心，清洗，提纯备用。请参考图3的(B)，图3的(B)为该步骤中制备出的中空聚合物微球的电子显微镜照片。
将200mg上述产物加入反应釜中，加入50％H2SO4溶液淹没上述产物，搅拌均匀后升温至120℃，加热12h；冷却至室温后加入冰水混合物中结晶，过滤提纯得到阳离子吸附剂，真空干燥后获得本申请所提供的阳离子染料吸附剂s-COP-P。
以相同的方法，分别采用式(8)和(9)所表示的单体制备阳离子染料吸附剂h-COP-P和阳离子染料吸附剂sh-COP-P，使用三种阳离子染料吸附剂分别对罗丹明染料进行吸附。请参考图4，图4为分别使用三种阳离子染料吸附剂吸附罗丹明染料的移除率的对比图。从图4可知，阳离子染料吸附剂s-COP-P、h-COP-P和sh-COP-P对罗丹明染料的移除率分别为40％-60％，60％-80％以及80％-100％。
实验结果证实，本申请所提供的阳离子染料吸附剂对阳离子染料的吸附效果佳。
相较于现有技术，本申请所提供的阳离子染料吸附剂由于中空的聚合物微球经过磺化处理，聚合物微球的表面含有丰富的磺酸基，在溶液中呈现负电性状态，通过静电吸附作用力，能够有效地高选择性地吸附阳离子染料。同时，中空的结构可以为聚合物微球提供更高的比表面积，相较于实心的聚合物微球具有更高的吸附力。
以上对本申请实施方式提供了详细介绍，本文中应用了具体个例对本申请的原理及实施方式进行了阐述，以上实施方式的说明只是用于帮助理解本申请。同时，对于本领域的技术人员，依据本申请的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本申请的限制。

Claims (10)

1.一种阳离子染料吸附剂，其特征在于，所述阳离子染料吸附剂包括中空聚合物微球，所述中空聚合物微球表面分散有磺酸基，所述中空聚合物微球的材料选自由下式(1)至(3)所表示的化合物中的一个或多个，
Figure FDA0002452253050000011
Figure FDA0002452253050000021
其中，n1、n2、n3为大于或者等于0的整数，在式(1)至(3)所表示的化合物中，环上的氢原子被取代基取代或者不被取代。
2.如权利要求1所述的阳离子染料吸附剂，其特征在于，所述中空聚合物微球的分子式如下式(4)至(6)的任一项所示：
Figure FDA0002452253050000022
Figure FDA0002452253050000031
其中，m1至m16为大于或者等于0的整数，且m1至m4不同时为0，m5至m12不同时为0，m13至m16不同时为0。
3.如权利要求1所述的阳离子染料吸附剂，其特征在于，所述磺酸基的浓度为1.5mmol/g至3.0mmol/g。
4.如权利要求1所述的阳离子染料吸附剂，其特征在于，所述中空聚合物微球的厚度为10nm至100nm。
5.如权利要求1所述的阳离子染料吸附剂，其特征在于，所述中空聚合物微球的内径位于50nm至1000nm的范围内。
6.一种阳离子染料吸附剂的制备方法，其特征在于，包括以下步骤：
将无机纳米粒子，单体以及催化剂分散于溶液中，在氩气氛围下加热反应，在所述无机纳米粒子表面形成一层聚合物，其中，所述单体选自由下式(7)至(9)所表示的化合物中的一个或多个，
Figure FDA0002452253050000041
在式(7)至(9)所表示的化合物中，环上的氢原子被取代基取代或者不被取代；
除去所述无机纳米粒子以形成中空聚合物微球；
对所述中空聚合物微球表面进行磺化处理，形成具有磺酸基的中空聚合物微球，获得所述阳离子染料吸附剂。
7.如权利要求6所述的阳离子染料吸附剂的制备方法，其特征在于，所述无机纳米粒子材料的摩尔量与所述单体的摩尔量的比例为200:1至10:1。
8.如权利要求6所述的阳离子染料吸附剂的制备方法，其特征在于，在所述无机纳米粒子表面形成一层聚合物的步骤中，反应温度为50℃至70℃，反应时间为24h-48h。
9.如权利要求6所述的阳离子染料吸附剂的制备方法，其特征在于，所述无机纳米粒子的粒径位于50nm到1000nm的范围内。
10.如权利要求6所述的阳离子染料吸附剂的制备方法，其特征在于，所述无机纳米粒子选自氧化铝、氧化锌、氧化钙、氧化镁的一种或多种。
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