Synthesis of smart dual-response oil-water separation material
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摘要: 智能材料是一种具有感知、响应和适应环境能力的材料。随着科技的不断发展，智能材料在各个领域的应用越来越广泛，未来的发展前景十分广阔。本文合成了一种含有羧基及可聚合基团的偶氮苯化合物，以该偶氮苯化合物作为光响应单元，甲基丙烯酸二甲氨乙酯作为pH响应单元，采用可逆加成-断裂链转移(RAFT)聚合与甲基丙烯酸羟乙酯进行一步共聚，得到了光和pH智能双响应三元共聚物。聚合物涂层在不同条件的刺激下接触角最大变化可达120.2°，经过亲水-疏水的多次转换，接触角仍可以恢复到初始状态，具有优异的可逆刺激响应能力。将聚合物涂敷在无纺布上制成光/pH双响应油水分离膜，该膜在亲油疏水与亲水疏油之间发生可逆转变，实现选择性油水分离，单次分离效率分别达96.3%和95.8%。这种对光和pH的刺激响应性使其可用于复杂环境的液体传输和油水分离等领域，具有巨大的智能水油分离应用潜力。Abstract: Smart materials are materials that have abilitys to sense, respond and adapt to their environments. With the continuous development of science and technology, smart materials are more and more widely used in various fields, and have very broad prospects for development in the future. In this paper, one kind of azobenzene compound containing polymerizable groups was synthesized. This azobenzene compound was used as photoresponsive unit and dimethylaminoethyl methacrylate as a pH responsive unit, they can copolymerize with hydroxyethyl methacrylate to form terpolymer by one step reversible addition-fragmentation chain transfer polymerization (RAFT) method, which has smart dual response to light and pH. When stimulated by different conditions, the maximum contact angle change of the polymer coating can reach 120.2°, and the contact angle can still restore to the initial state after multiple transformations between hydrophilic and hydrophobic. It shows that the material has excellent reversible stimulus responsiveness ability. When the polymer was coated on the non-woven fabric to make light /pH dual-responsive oil-water separation membrane, it can undergo a reversible transition between hydrophilic and hydrophobic, so as to achieve the selective separation of oil and water, the single separation efficiency can reach 96.3% and 95.8%, respec-tively. This kind of stimulus responsibility to light and pH can be used in areas such as liquid transport and oil-water separation in complex environments, and have great potential for smart water-oil separation application.
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图 1 偶氮苯单体及聚合物的合成路线 (a,b: 中间体, c:单体, d: 聚合物)
Figure 1. Synthetic route of azobenzene monomer and polymer (a,b: intermediate, c: monomer, d: polymer)
图 2 中间体a、b，单体c和聚合物d的傅里叶红外谱图
Figure 2. FT-IR of azobenzene intermediates a,b, monomer c and polymer d
图 5 无纺布的SEM图像(a)；油水分离膜的SEM图像(b)
Figure 5. SEM image of blank non-woven fabric (a); SEM image of oil-water separation membrane (b)
图 6 聚合物d的载玻片涂层在不同条件下的接触角变化: (a) 自然条件下; (b) 经pH=3缓冲溶液浸泡后; (c) 经pH=10缓冲溶液浸泡后; (d) 经365 nm光照射后; (e) 经445 nm光照射后； (f) 经pH=3缓冲溶液浸泡并用365 nm紫外光照射后
Figure 6. Contact angle variation of polymer d slide coatings under different conditions: (a) the natural state; (b) after immersion with pH=3 buffer solution; (c) after immersion in pH=10 buffer solution; (d) after exposure to 365 nm light; (e) after exposure to 445 nm light; (f) after immersion in pH=3 buffer solution and irradiation with 365 nm ultraviolet light
图 7 聚合物d的载玻片涂层在不同pH和光照下的接触角的可逆变化情况
Figure 7. Contact angle reversible variation of polymer d slide coatings under different pH and light conditions
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