功能性柔性聚合物Janus纳米片的制备及性能研究

发布时间：2018-03-22 19:52

  本文选题：温度响应性　切入点：Janus纳米片　出处：《辽宁大学》2017年硕士论文　论文类型：学位论文

【摘要】：Janus材料由于独特的不对称性质具有广泛的应用前景而深受科研人员的关注。聚合物Janus片状材料,兼具Janus材料的不对称性和聚合物的柔性与可塑性,而且片状形貌加强了其不对称性能。本文利用聚合物Janus片状材料的可塑性为其增加了温度响应性和离子响应性。首先通过模板法制备了温度响应性的聚合物Janus纳米囊,打碎得到Janus纳米片。验证了Janus纳米片具有温度响应性,并且可以用作颗粒乳化剂,稳定油/水乳液。主要工作内容如下:1.本文使用St?ber法制备得到了SiO_2纳米微球,以SiO_2纳米微球为牺牲模板,先后进行氨基化改性和溴化改性,使其变成ATRP引发剂。通过ATRP活性自由基聚合接枝具有疏水性能的聚甲基丙烯酸叔丁酯(PtBMA),然后以N,N-亚甲基双丙烯酰胺(MBA)作为交联剂,进行第二次ATRP活性自由基聚合接枝具有温度响应性的聚乙烯己内酰胺(PNVCL),得到SiO_2复合纳米微球。最后用氢氟酸刻蚀掉SiO_2内核,得到温度响应性Janus囊,超声打碎后得到温度响应性Janus纳米片。通过FT-IR、Zeta电位、EDX、TGA、SEM、TEM等表征方式对Janus纳米片的形貌和组成做了表征。通过温度条件的调节,测试了Janus纳米片的温度响应性。从宏观观测了Janus纳米片不同温度条件下在超纯水中的分散状态的变化,从微观观测不同温度条件下Janus纳米片在扫描电镜下的不同形貌变化,验证Janus纳米片的温度响应性。通过调节温度条件,测定Janus纳米片对油/水乳液的乳化性能,当环境温度适宜时用光学显微镜观察其乳化性能,然后通过改变温度,检测其温度响应性所致的乳化性能衰减直至破乳。2.首先合成了溴化1-乙烯基-3-乙基咪唑离子液体(EVImBr)。然后将氨基化的硅球,继续羟基化改性。通过硅球表面的羟基引发己内酯的开环聚合,接枝具有疏水性能的聚己内酯(PCL),然后将聚己内酯末端的羟基溴化改性成大分子ATRP引发剂。然后以N,N-亚甲基双丙烯酰胺(MBA)作为交联剂再经ATRP活性自由基聚合接枝聚溴化1-乙烯基-3-乙基咪唑离子液体(PEVIm Br)。得到SiO_2复合纳米微球。最后用氢氟酸刻蚀掉SiO_2纳米微球得到离子液体基Janus纳米中空微球。将离子液体基Janus纳米中空微球用超声波细胞粉碎机打碎,得到离子液体基Janus纳米片。
[Abstract]:Because of its unique asymmetric properties, Janus materials have attracted much attention from researchers. Polymer Janus lamellar materials have both asymmetry of Janus materials and flexibility and plasticity of polymers. In this paper, the plasticity of polymer Janus sheet material is used to increase its temperature response and ion response. Firstly, the thermo-responsive polymer Janus nanocapsules were prepared by template method. Janus nanoparticles were obtained by breaking. It was proved that Janus nanoparticles have temperature response and can be used as particle emulsifiers to stabilize oil / water emulsions. The main work is as follows: 1. SiO_2 nanospheres were prepared by ber method. Using SiO_2 nanospheres as sacrificial template, the amination modification and bromination modification were carried out successively. It was turned into ATRP initiator, and ATRP was grafted onto poly (tert-butyl methacrylate) with hydrophobic properties by ATRP active radical polymerization, and then Nn- methylene bisacrylamide (MBA) was used as crosslinking agent. The second ATRP active radical polymerization was carried out to graft polyvinylcaprolactam (PNVCLN) with temperature response to obtain SiO_2 composite nanospheres. Finally, the core of SiO_2 was etched by hydrofluoric acid, and a temperature responsive Janus capsule was obtained. The temperature responsive Janus nanocrystals were obtained by ultrasonic analysis. The morphology and composition of Janus nanoparticles were characterized by means of FT-IRN Zeta potential and EDX TGA SEMMA-TEM. The morphology and composition of Janus nanoparticles were characterized by adjusting the temperature conditions. The temperature response of Janus nanocrystals was tested. The dispersion state of Janus nanoparticles in ultrapure water at different temperatures was observed macroscopically, and the morphology of Janus nanocrystals at different temperatures was observed under scanning electron microscope. To verify the temperature response of Janus nanoparticles, the emulsifying properties of Janus nanoparticles to oil / water emulsions were determined by adjusting the temperature conditions, and the emulsifying properties of Janus nanoparticles were observed by optical microscope when the ambient temperature was suitable, and then by changing the temperature, The emulsifying properties due to its temperature response were measured to demulsification .2.Firstly, 1-vinyl-3-ethylimidazolium bromide ionic liquid (EVImBran) was synthesized. Continuous hydroxylation modification. The ring-opening polymerization of caprolactone was initiated by hydroxyl groups on the surface of silicon spheres. Poly (caprolactone) with hydrophobicity was grafted onto ATRP, then the hydroxyl bromide at the end of the polycaprolactone was modified into a macromolecular ATRP initiator. N- (N-methylene bisacrylamide) was then used as the crosslinking agent and then grafted by ATRP active radical polymerization. SiO_2 composite nanospheres were obtained from 1-vinyl-3-ethylimidazolium bromide ionic liquid. Finally, SiO_2 nanospheres were etched by hydrofluoric acid to obtain ionic liquid-based Janus hollow microspheres. The ultrasonic cell crusher broke, Ionic liquid based Janus nanoparticles were obtained.
【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;TQ317

【参考文献】

中国期刊全文数据库 前1条

1 康力敏;刘恩周;吴丰;张增庆;胡晓云;姜振益;樊君;;银表面等离子体效应增强TiO_2纳米管阵列光解水制氢[J];化工进展;2012年S1期

，

本文编号：1650136