超疏水苯并噁嗪<strong>-ZnO</strong>改性海绵的制备及其油水分离性能

doi:10.11901/1005.3093.2023.094

材料研究学报

2024, Vol. 38

Issue (1): 71-80 DOI: 10.11901/1005.3093.2023.094

研究论文

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超疏水苯并噁嗪-ZnO改性海绵的制备及其油水分离性能

李宇轩¹, 杜永刚¹, 苏俊铭¹, 王智²(

), 朱永飞¹(

)

1 南宁师范大学化学与材料学院广西天然高分子化学与物理重点实验室南宁 530001
2 中北大学材料科学与工程学院太原　030051

Superhydrophobic Sponge Coated with Polybenzoxazine and ZnO for Oil-Water Separation

LI Yuxuan¹, DU Yonggang¹, SU Junming¹, WANG Zhi²(

), ZHU Yongfei¹(

)

1 Guangxi Key Laboratory of Natural Polymer Chemistry and Physics, College of Chemistry and Materials, Nanning Normal University, Nanning 530001, China
2 School of Materials Science and Engineering, North University of China, Taiyuan 030051, China

引用本文:

李宇轩, 杜永刚, 苏俊铭, 王智, 朱永飞. 超疏水苯并噁嗪-ZnO改性海绵的制备及其油水分离性能[J]. 材料研究学报, 2024, 38(1): 71-80.
Yuxuan LI, Yonggang DU, Junming SU, Zhi WANG, Yongfei ZHU. Superhydrophobic Sponge Coated with Polybenzoxazine and ZnO for Oil-Water Separation[J]. Chinese Journal of Materials Research, 2024, 38(1): 71-80.

全文: PDF(8987 KB) HTML

摘要:

先用腰果酚和十二胺制备苯并噁嗪(Cd-D)，然后用水热法和浸涂法依次将ZnO微/纳米结构和Cd-D负载在三聚氰胺甲醛海绵(MS)表面，制备出超疏水MS(PCd-D/ZnO/MS)。当水热反应中Zn(NO₃)₂浓度为0.03 mol/L、Zn(NO₃)₂与六次甲基四胺的摩尔比为1∶2、反应时间和温度分别为4 h和95℃时，制备出的改性MS水接触角(WCA)可达153.6°。PCd-D/ZnO/MS对有机溶剂和油类具有较高的吸附量(48.19~113.44 g/g)和极高的吸附速率。同时，聚苯并噁嗪、ZnO与MS之间产生的多种相互作用(氢键、配位键和化学键等)使表面改性结构牢固地粘附在MS骨架上，从而使PCd-D/ZnO/MS具有优异的重复使用性能。PCd-D/ZnO/MS循环使用30次后仍保持超疏水性和96.6%的吸附量，重复使用100次后其WCA可达147.3°、吸油量保持为92.6%。PCd-D/ZnO/MS在真空泵的辅助下可连续用于油水分离，分离效率高于90%。PCd-D/ZnO/MS还具有优异的耐酸、碱、盐性能，在强碱溶液中浸泡30 d后仍保持超疏水性。

关键词 ：有机高分子材料, 苯并噁嗪, ZnO, 超疏水海绵, 油水分离

Abstract：

The discharge of industrial and daily life waste water, as well as the oil leakage not only cause serious environmental disaster but also the waste of resources. Superhydrophobic sponge is a kind of ideal materials of separating and recovering oil/water mixture. Herein, benzoxazine based on renewable cardanol and dodecamine (Cd-D) was synthesized, then ZnO micro-/nano-structure and Cd-D were successively coated on the surface of melamine sponge (MS) by a simple hydrothermal process and dip-coating method to prepare superhydrophobic MS (PCd-D/ZnO/MS). A water contact angle (WCA) of 153.6° could be obtained when the concentration of Zn(NO₃)₂ was 0.03 mol/L and the mole ratio of Zn(NO₃)₂ and HMTA was 1:2 prepared at 95^oC for 4 h. PCd-D/ZnO/MS exhibited a high oil absorption capacity (48.19~113.44 g/g) for organic solvents and oils with a rapid absorption rate. In addition, polybenzoxazine and ZnO (or MS) could form multiple interactions (including hydrogen bond, coordination bond, chemical bond, etc.), which made the coating be firmly adhered to the MS skeleton and thus endowed PCd-D/ZnO/MS excellent reusability. PCd-D/ZnO/MS could maintain superhydrophobicity and 96.6% of initial adsorption capacity after 30 cycles, the WCA of the modified MS could reach 147.3° with an absorption retention of 92.6% after 100 cycles. With the help of vacuum pump, PCd-D/ZnO/MS could be used for continuous oil/water separation with a separation efficiency of above 90%. Moreover, PCd-D/ZnO/MS showed excellent resistance to strong acid, alkali and salt, and then still displayed superhydrophobicity even being immersed in NaOH solution for 30 days. In summary, PCd-D/ZnO/MS not only possessed a simple, safe and economical preparation processe but also exhibited excellent oil-water separation ability, reusability and resistance to acid, alkali and salt, which made PCd-D/ZnO/MS a promising oil-water separation material.

Key words： organic polymer materials benzoxazine ZnO superhydrophobic sponge oil-water separation

收稿日期: 2023-01-11

ZTFLH:

TQ323

基金资助:国家自然科学基金(51773185);国家自然科学基金(U1810118)

通讯作者: 朱永飞，教授，yonfez@163.com，研究方向为苯并噁嗪的制备及应用;
王智，教授，hugh-wang@nuc.edu.cn，研究方向为苯并噁嗪树脂的合成以及改性

Corresponding author: ZHU Yongfei, Tel: (0771)3908065, E-mail: yonfez@163.com;
WANG Zhi, Tel: (0771)3908065, E-mail: hugh-wang@nuc.edu.cn

作者简介: 李宇轩，男，1999年，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2023.094 或 https://www.cjmr.org/CN/Y2024/V38/I1/71

图1 Cd-D的合成路线及其固化物(PCd-D)结构

图2 PCd-D/ZnO/MS的制备流程

图3 Zn(NO3)2、Zn(NO3)2与HMTA摩尔比、反应时间以及反应温度对PCd-D/ZnO/MS水接触角(WCA)的影响

图4 原始MS、ZnO/MS和PCd-D/ZnO/MS的SEM照片

图5 PCd-D/ZnO/MS的 XRD谱

图6 原始MS的XPS全图谱、C1s谱图、O1s谱图和、N 1s谱

图7 PCd-D/ZnO/MS的XPS全谱图、C1s谱图、O1s谱图和N 1s谱

表1 MS与PCd-D/ZnO/MS的C1s和N1s解析数据

图8 MS和PCd-D/ZnO/MS在水中的照片、水和大豆油滴在MS和PCd-D/ZnO/MS的表面状态

图9 PCd-D/ZnO/MS对不同有机溶剂和油类的吸附能力

图10 PCd-D/ZnO/MS分离甲苯/水混合物和二氯甲烷/水混合物以及PCd-D/ZnO/MS对大豆油/水混合物的连续分离

图11 PCd-D/ZnO/MS循环使用不同次数后的吸油量和水接触角

图12 PCd-D/ZnO/MS在HCl和NaOH溶液中浸泡不同时间后的WCA

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