CN106947339A - 一种基于改性二氧化钛的光降解甲醛膜 - Google Patents

一种基于改性二氧化钛的光降解甲醛膜 Download PDF

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CN106947339A
CN106947339A CN201710253612.5A CN201710253612A CN106947339A CN 106947339 A CN106947339 A CN 106947339A CN 201710253612 A CN201710253612 A CN 201710253612A CN 106947339 A CN106947339 A CN 106947339A
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tio
film
carboxyl
nano
titanium dioxide
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周永南
刘波
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Great Rich Technology Co Ltd
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Abstract

本发明公开了一种基于改性二氧化钛的光降解甲醛膜，属于膜技术领域。本发明在配置硬化液涂层的同时制备改性二氧化钛，将改性二氧化钛更好地分散于汽车膜、建筑膜、家居膜等产品的硬涂层中，不仅简化了工艺、节约了成本，而且得到的光降解甲醛膜在不影响原有汽车膜、建筑膜、家居膜的性能的基础上又可以起到降解甲醛的作用。

Description

一种基于改性二氧化钛的光降解甲醛膜
技术领域
本发明涉及一种基于改性二氧化钛的光降解甲醛膜，属于膜技术领域。
背景技术
室内甲醛污染对人类生活造成巨大威胁，包括在建筑居住空间内和在汽车之类的密闭空间内。室内甲醛主要来源于室内装修物以及一些皮制制品，还有各种不符合国家生产标准的非法材料。我国规定，室内甲醛含量不能超过0.08mg/m3，高浓度甲醛会引起眼部、咽喉不适、胸闷、气喘、皮炎等，还有可怕的致癌风险。
目前，市面上现有的治理甲醛污染的方法很多，例如微生物降解法、植物净化、化学反应方法、物理吸附技术、纳米光催化技术等。但是微生物降解法不能长久使用；植物净化法摆放过多，夜间使房内的二氧化碳浓度过高，影响健康；化学反应方法自身会造成化学污染；物理吸附方法需要消耗多余的能耗，增加成本；而纳米光催化技术降解甲醛环保、安全、高效、耗能小。
二氧化钛(TiO2)为代表的光催化剂受到人们的广泛关注。目前通过掺杂改性光催化剂TiO2，增强其对可见光的吸收能力，是一种开发具有可见光催化活性的催化材料的有效途径。但一般掺杂改性工艺复杂，需要高温煅烧，而且所得催化剂的吸附性能和可见光催化性能均较差，因此开发工艺简单、具有强吸附能力和高可见光催化活性的掺杂型TiO2光催化剂并将其用于制备光催化降解甲醛膜，在能源利用和环境治理方面都具有重要的意义。
目前的光催化降解甲醛膜多为过滤膜，并非实质上的光催化降解甲醛膜；其他一些治理甲醛技术多是一些空气净化器、喷剂、或是涂料。目前市面上的只有TiO2喷剂，产品效率不高且使用寿命很短，干燥后会被风、自然力，人为接触刮擦等破坏，从原有的负载物上消失。
在前期研究过程中，发明人开发了一种光催化降解甲醛膜，通过直接将纳米TiO2分散液加入到汽车膜、建筑膜、家居膜等产品的硬涂层中，达到了既不影响原有汽车膜、建筑膜、家居膜的性能，又可以起到降解甲醛的效果。然而，制备得到的膜的催化降解性能还有待进一步改善。此外，这种方式需要先制备光催化剂或者购买光催化剂，存在工艺繁琐或成本不节约的问题。
发明内容
为了解决上述问题，本发明提供了一种基于改性二氧化钛的光降解甲醛膜及其制备方法，本发明在配置硬化液涂层的同时制备改性二氧化钛，将改性二氧化钛更好地分散于汽车膜、建筑膜、家居膜等产品的硬涂层中，不仅简化了工艺、节约了成本，而且得到的光降解甲醛膜在不影响原有汽车膜、建筑膜、家居膜的性能的基础上又可以起到降解甲醛的作用。
本发明的基于改性二氧化钛的光降解甲醛膜的制备方法，所述制备方法包括：(1)配置一定浓度的安装胶，在基材一侧表面均匀涂覆安装胶；(2)在羧基功能化富勒烯衍生物中加入纳米TiO2、基础硬涂层组分，超声分散1-2h，得到分散均匀的含有改性TiO2的硬化液涂层；(3)硬化液涂层进一步进行上机涂覆，涂覆在基材的另一侧表面形成硬涂层。
在一种实施方式中，所述基于改性二氧化钛的光降解甲醛膜依次包括分散有改性TiO2的硬涂层、基材层、安装胶层、离型膜层。
在一种实施方式中，所述羧基功能化富勒烯衍生物的制备具体是：氮气保护下，将富勒烯C60、对羧基苯甲醛和肌氨酸在甲苯中100-115℃反应8-10小时，用水洗涤所得固体，烘干，得到羧基功能化富勒烯衍生物。
在一种实施方式中，所述富勒烯C60、对羧基苯甲醛、肌氨酸与甲苯的配比为1mol：10mol：10mol：30mL。
在一种实施方式中，所述羧基功能化富勒烯衍生物、纳米TiO2的质量比为1:50～1:200。
在一种实施方式中，所述羧基功能化富勒烯衍生物、纳米TiO2的质量比为1:200。
在一种实施方式中，所述基础硬涂层组分主要成分为UV光固化型的丙烯酸树脂。UV光固化型的丙烯酸树脂产品寿命长，老化硬涂层硬度达到3H、浊度小于3％，产品清晰度高。
在一种实施方式中，所述纳米TiO2的粒径为15nm～100nm。
在一种实施方式中，所述纳米二氧化钛为P25-TiO2。
在一种实施方式中，所述纳米TiO2的质量为基础硬涂层组分中丙烯酸树脂质量的7％～9％。
在一种实施方式中，所述纳米TiO2的质量为基础硬涂层组分中丙烯酸树脂质量的8％。
在一种实施方式中，所述基础硬涂层组分中，按质量份数计，含有丙烯酸树脂8～12份、溶剂乙酸乙酯12～18份、附着力促进剂0.08～0.12份、光稳定剂0.08～0.12份、光引发剂0.08～0.12份。
在一种实施方式中，所述基础硬涂层组分中，按质量份数计，含有丙烯酸树脂10份、溶剂乙酸乙酯15份、附着力促进剂0.1份、光稳定剂0.1份、光引发剂0.1份。
在一种实施方式中，所述步骤(2)具体是：首先在羧基功能化富勒烯衍生物中加入纳米TiO2、溶剂乙酸乙酯并超声分散0.8-1.2h；再加入丙烯酸树脂，超声分散0.1-0.4h；再加入附着力促进剂、光稳定剂、光引发剂超声分散0.1-0.4h，得到分散均匀的含有改性TiO2的硬化液涂层；硬化液涂层进一步进行上机涂覆，涂覆在基材的一侧表面形成硬涂层。
在一种实施方式中，所述硬涂层的厚度为1～5μm。
在一种实施方式中，所述基材层的材料为PET、PE、PVC、PP、PC及TPU等中的任意一种或者两种以上组合。
在一种实施方式中，所述安装胶层的材料为丙烯酸酯树脂、聚氨酯树脂、硅胶树脂等中的任意一种或者两种以上组合。
在一种实施方式中，所述安装胶层的厚度为5～15μm。可根据客户或者特定产品要求，控制控制安装胶厚度或安装胶材料种类来控制剥离力大小。
在一种实施方式中，所述安装胶层主要用来贴合安装。
在一种实施方式中，所述离型膜为硅离型膜、氟离型膜等中任意一种。
在一种实施方式中，所述离型膜主要用来保护安装胶。
本发明的第二个目的是提供按照上述方法制备得到的改性二氧化钛的光降解甲醛膜及其在家居、建筑、汽车等方面的应用。
本发明的优点和效果：
(1)本发明将改性TiO2加入到汽车膜、建筑膜、家居膜的硬涂层中，提高了光降解甲醛膜的催化降解效果，同时产品硬度达到3H、耐刮性能强，并不会被风、自然力，人为接触刮擦等破坏，大大提高了产品寿命。降解甲醛膜可以使用2年以上。
(2)本发明方法，直接在制备改性TiO2的同时制备得到硬涂层涂料，一方面不需要预先制备改性好的TiO2或者购买改性好的TiO2，与现有的改性TiO2的制备相比工艺更加简单，另一方面也缩短了时间、节约了成本。
(3)本发明方法中，直接利用基础硬涂层组分中的溶剂乙酸乙酯，在超生条件下分散羧基功能化富勒烯衍生物和纳米TiO2进行超声分散，在形成改性TiO2的同时使得形成的改性TiO2也顺利地分散在溶剂中，可以减少后续处理的时间；由于本方法中不需要额外添加其他的试剂，也就免除了额外的试剂去除步骤，防止了额外引入的试剂对整个体系的影响，保证了得到的光降解甲醛膜的性能。
(4)在羧基功能化富勒烯衍生物、纳米TiO2的用量比为1:200下，达到最佳效果；当羧基功能化富勒烯衍生物添加过多会明显影响膜的透明性，而添加过少会导致甲醛降解效果无明显改善。
具体实施方案
下面是对本发明进行具体描述。
实施例1：改性二氧化钛光催化降解甲醛膜的制备
按照以下方法制备改性二氧化钛光催化降解甲醛膜：
(1)配置一定浓度的安装胶；
(2)在基材一侧表面均匀涂覆安装胶；安装胶厚度为10μm左右；
(3)制备含有改性TiO2的硬化液涂层，具体是：
先氮气保护下，将富勒烯C60、对羧基苯甲醛和肌氨酸在甲苯中100-115℃反应8-10小时，用水洗涤所得固体，烘干，得到羧基功能化富勒烯衍生物；
在羧基功能化富勒烯衍生物中加入0.8份纳米TiO2(P25-TiO2)、溶剂乙酸乙酯15份并超声分散0.8h；再加入10份丙烯酸树脂，超声分散0.5h；再加入0.1份附着力促进剂、0.1份光稳定剂、0.1份光引发剂超声分散0.2h，得到分散均匀的含有改性TiO2的硬化液涂层。
其中，羧基功能化富勒烯衍生物、纳米TiO2的质量比为1:200。
(4)硬化液涂层进一步进行上机涂覆，涂覆在基材的一侧表面形成硬涂层；控制烘箱温度80°，光照强度280mJ/cm2，线速度30m/min，根据工艺即可以得到不同厚度，比如的厚度为1～5μm的改性二氧化钛光降解甲醛膜。
实施例2：改性二氧化钛光催化降解甲醛膜的制备
与实施例1相比，羧基功能化富勒烯衍生物、纳米TiO2的质量比为1:50，其他步骤或者参数与实施例1一致。
实施例3：改性二氧化钛光催化降解甲醛膜的制备
与实施例1相比，羧基功能化富勒烯衍生物、纳米TiO2的质量比为1:100，其他步骤或者参数与实施例1一致。
实施例4：改性二氧化钛光催化降解甲醛膜的制备
与实施例1相比，羧基功能化富勒烯衍生物、纳米TiO2的质量比为1:150，其他步骤或者参数与实施例1一致。
实施例5：改性二氧化钛光催化降解甲醛膜的制备
与实施例1相比，羧基功能化富勒烯衍生物、纳米TiO2的质量比为1:250，其他步骤或者参数与实施例1一致。
对照例1：
按照以下方法制备光催化降解甲醛膜：
(1)配置一定浓度的安装胶；
(2)在基材一侧表面均匀涂覆安装胶；安装胶厚度为10μm左右；
(3)制备含有改性TiO2的硬化液涂层，具体是：
加入0.8份纳米TiO2(P25-TiO2)、溶剂乙酸乙酯15份并超声分散0.8h；再加入10份丙烯酸树脂，超声分散0.5h；再加入0.1份附着力促进剂、0.1份光稳定剂、0.1份光引发剂超声分散0.2h，得到分散均匀的含有纳米TiO2的硬化液涂层。
(4)硬化液涂层进一步进行上机涂覆，涂覆在基材的一侧表面形成硬涂层；控制烘箱温度80°，光照强度280mJ/cm2，线速度30m/min，根据工艺即可以得到不同厚度，比如的厚度为1～5μm的硬涂层中分散有纳米TiO2的光降解甲醛膜。
对照例2：
按照以下方法制备改性二氧化钛光催化降解甲醛膜：
(1)配置一定浓度的安装胶；
(2)在基材一侧表面均匀涂覆安装胶；安装胶厚度为10μm左右；
(3)制备含有改性TiO2的硬化液涂层，具体是：
先氮气保护下，将富勒烯C60、对羧基苯甲醛和肌氨酸在甲苯中100-115℃反应8-10小时，用水洗涤所得固体，烘干，得到羧基功能化富勒烯衍生物；将20毫克羧基功能化富勒烯衍生物和1克二氧化钛(P25-TiO2)分散到50毫升无水乙醇中，所得溶液利用超声波分散30分钟后，旋转蒸发缓慢除去溶剂，将所得固体在真空干燥箱中烘干即得到富勒烯掺杂二氧化钛光催化剂；
在富勒烯掺杂二氧化钛光催化剂0.8份、溶剂乙酸乙酯15份并超声分散0.8h；再加入10份丙烯酸树脂，超声分散0.5h；再加入0.1份附着力促进剂、0.1份光稳定剂、0.1份光引发剂超声分散0.2h，得到分散均匀的含有改性TiO2的硬化液涂层。
(4)硬化液涂层进一步进行上机涂覆，涂覆在基材的一侧表面形成硬涂层；控制烘箱温度80°，光照强度280mJ/cm2，线速度30m/min，根据工艺即可以得到不同厚度，比如的厚度为1～5μm的改性二氧化钛光降解甲醛膜。
发明人比较了按照实施例1-3及对照例1-2得到的硬涂层表面积为1m2、厚度为5μm的光降解甲醛膜对甲醛的降解效果，结果如表1所示。结果显示，本实施例1-4方法得到的基于改性二氧化钛的光降解甲醛膜，比使用普通二氧化钛得到的甲醛膜相比，对甲醛的降解效果得到了显著的提高，同时还保证了较好的产品透明性。同时，以上数据显示，在羧基功能化富勒烯衍生物、纳米TiO2的用量比为1:200下，达到最佳效果；当羧基功能化富勒烯衍生物添加过多会明显影响膜的透明性，而添加过少会导致甲醛降解效果无明显改善。另外，发明人先制备富勒烯掺杂二氧化钛光催化剂再将其用于制备光催化降解甲醛膜(对照例2)，结果发现，对甲醛的降解效果和产品透过率都要明显低于实施例1得到的产品，这可能是由于已经改性好的二氧化钛，存在空间结构位阻等问题，导致在乙酸乙酯中的分散性能反而受限并影响到了催化性能的发挥。
表1对甲醛的降解效果
项目 实验条件下的降解率(％) 产品透过率
实施例1 92.7％ 90％
实施例2 85.2％ 78％
实施例3 85.1％ 82％
实施例4 87.9％ 88％
实施例5 77.3％ 90％
对照例1 76.1％ 90％
对照例2 82.2％ 86％
注：将样品0.8mg放于1立方米实验舱中，加热挥发污染物，使样品浓度达0.8mg/m3，日光灯照射24h，采样检测污染物浓度(检测方法参照JC/T 1074-2008)，计算去除率。
此外，本实施例1-4方法得到的基于改性二氧化钛的光降解甲醛膜，硬度达到3H、耐刮性能强，并不会被风、自然力，人为接触刮擦等破坏。另外，由于硬涂层厚度5μm合适，不容易折断，在基材层表面的附着力较高，可长期使用，可以适用于制备汽车膜、建筑膜、家居膜等。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (10)

1.一种基于改性二氧化钛的光降解甲醛膜的制备方法，其特征在于，所述制备方法包括：(1)配置一定浓度的安装胶，在基材一侧表面均匀涂覆安装胶；(2)在羧基功能化富勒烯衍生物中加入纳米TiO2、基础硬涂层组分，超声分散1-2h，得到分散均匀的含有改性TiO2的硬化液涂层；(3)硬化液涂层进一步进行上机涂覆，涂覆在基材的另一侧表面形成硬涂层。
2.根据权利要求1所述的方法，其特征在于，所述羧基功能化富勒烯衍生物、纳米TiO2的质量比为1:50～1:200。
3.根据权利要求1所述的方法，其特征在于，所述羧基功能化富勒烯衍生物、纳米TiO2的质量比为1:200。
4.根据权利要求1所述的方法，其特征在于，所述羧基功能化富勒烯衍生物的制备具体是：氮气保护下，将富勒烯C60、对羧基苯甲醛和肌氨酸在甲苯中100-115℃反应8-10小时，用水洗涤所得固体，烘干，得到羧基功能化富勒烯衍生物。
5.根据权利要求1所述的方法，其特征在于，所述基础硬涂层组分中，按质量份数计，含有丙烯酸树脂8～12份、溶剂乙酸乙酯12～18份、附着力促进剂0.08～0.12份、光稳定剂0.08～0.12份、光引发剂0.08～0.12份。
6.根据权利要求1所述的方法，其特征在于，所述纳米TiO2的质量为基础硬涂层组分中丙烯酸树脂质量的7％～9％。
7.根据权利要求1所述的方法，其特征在于，所述步骤(2)具体是：首先在羧基功能化富勒烯衍生物中加入纳米TiO2、溶剂乙酸乙酯并超声分散0.8-1.2h；再加入丙烯酸树脂，超声分散0.1-0.4h；再加入附着力促进剂、光稳定剂、光引发剂超声分散0.1-0.4h，得到分散均匀的含有改性TiO2的硬化液涂层；硬化液涂层进一步进行上机涂覆，涂覆在基材的一侧表面形成硬涂层。
8.根据权利要求1-7任一所述方法得到的光降解甲醛膜。
9.权利要求8所述的光降解甲醛膜的应用。
10.根据权利要求9所述的应用，其特征在于，所述应用是应用于家居、建筑或汽车方面。
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CN109939732A (zh) * 2019-03-26 2019-06-28 中国科学院化学研究所 富勒烯衍生物修饰的半导体复合材料在光催化降解甲醛中的应用
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