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ATRP法制備離子交換膜應(yīng)用于擴散滲析和電滲析

發(fā)布時間:2018-06-12 09:21

  本文選題:原子轉(zhuǎn)移自由基聚合 + 陽離子交換膜。 參考:《合肥工業(yè)大學》2015年碩士論文


【摘要】:在現(xiàn)代工業(yè)如鋼鐵、冶金等行業(yè)生產(chǎn)過程中,常常會產(chǎn)生大量廢液。如果這些廢液沒有處理就直接排放,不但浪費了廢液中的有用資源,而且會嚴重污染環(huán)境和水源。擴散滲析(DD)是一種低操作費用的分離過程,驅(qū)動離子透過膜的動力主要是滲透側(cè)和擴散側(cè)的濃度差,因而能耗很低。DD過程還具有清潔、易操作等優(yōu)點。因此DD是解決廢液問題的一種簡單有效且經(jīng)濟環(huán)保的方法。另外,近年來許多特種分離領(lǐng)域的應(yīng)用需求亟需滿足,例如海水淡化過程往往希望離子交換膜能夠?qū)崿F(xiàn)不同價態(tài)離子的選擇性分離,從復(fù)雜的水鹽溶液中分離特定的離子。電滲析(ED)是在直流電場的作用下,離子透過離子交換膜進行遷移的過程,具有能耗低、操作簡便、使用壽命長、無污染等特點。在ED過程中,選擇透過性膜對不同價態(tài)離子的傳輸性能不同,從而使其分離。因此,制備出相應(yīng)的選擇性離子交換膜對電滲析分離一二價離子具有重大的意義。普通原子轉(zhuǎn)移自由基聚合(ATRP)以及電子轉(zhuǎn)移活化再生催化劑原子轉(zhuǎn)移自由基聚合(ARGET-ATRP)是近年來迅速發(fā)展并具有重要應(yīng)用價值的活性聚合方法,這種方法不僅可以控制聚合物的分子量和聚合鏈的多分散性,而且對聚合物的組成、結(jié)構(gòu)和端基官能團也實現(xiàn)了控制。通過這種方法還可以制備預(yù)定結(jié)構(gòu)和序列的嵌段和接枝共聚物。本論文一共包括五章。第一章是緒論,大體分為兩個部分。第一部分介紹目前工業(yè)廢液的危害和常規(guī)處理辦法,擴散滲析(DD)方法、裝置以及ATRP、 ARGET-ATRP。第二部分介紹一二價離子選擇性膜的應(yīng)用價值、制備方法以及電滲析(ED)等。第二章探索通過幾種ATRP方法制備聚苯乙烯磺酸鈉(PSSS)。包括:利用普通ATRP方法通過2-溴代異丁酸乙酯(EBiB)引發(fā)苯乙烯磺酸鈉(SSS)聚合;以溴化聚(2,6-二甲基-1,4-苯醚)(BPPO)上的PPO-CH2Br為大分子引發(fā)劑,通過ARGET ATRP聚合,在BPPO高分子鏈上接枝引入SSS;以及利用EBiB引發(fā)SSS進行ARGET ATRP聚合。前兩種方法都存在一定的不足,第三種方法可以成功制備得到聚電解質(zhì)(PSSS)。第三章將聚電解質(zhì)(PSSS)與聚乙烯醇(PVA)共混,并用硅烷偶聯(lián)劑交聯(lián),涂膜后干燥、熱處理得到陽離子交換膜。我們從水含量、65℃水中溶脹性能、離子交換容量(IEC)等方面對膜的性能進行表征,并將其應(yīng)用于擴散滲析(DD)過程,處理模擬工業(yè)廢水(NaOH/Na2WO4)體系。膜中PVA基體親水性較強,且能提供大量羥基(-OH),對水合離子如OH-的滲析通量較高;PSSS組分含有大量離子交換基團,提高了膜的滲析通量和離子選擇分離特性;硅烷偶聯(lián)劑可以進行交聯(lián),克服了膜溶脹度高的缺點。第四章講述了通過SI-ATRP方法在商業(yè)溴化聚(2,6-二甲基-1,4-苯醚)(BPPO)膜上接枝聚合SSS,再對BPPO基體進行季銨化。這樣膜的主體帶有大量的正電荷(-N+(CH3)3),而表面接枝了一層負電荷(-S03-)。我們從水含量、離子交換容量(IEC)、熱穩(wěn)定性、離子遷移數(shù)等方面對膜進行表征,并通過對NaCl/Na2SO4體系進行電滲析(ED)探究,考察膜對一二價陰離子的分離選擇性能。第五章是對全文的總結(jié)。對如何通過ATRP方法制備離子交換膜,以及該種膜在DD和ED應(yīng)用前景等方面進行了分析和總結(jié),得出一些有意義的結(jié)論。
[Abstract]:In the production process of modern industry, such as iron and steel, metallurgy and other industries, a lot of waste liquid is often produced. If the waste liquid is not treated, it will be discharged directly, not only waste the useful resources in the waste liquid, but also seriously pollute the environment and water source. Diffusion dialysis (DD) is a low operating cost separation process, the driving ion transmission through the membrane is the main power. It is the poor concentration of the osmotic side and the diffusion side, so the energy consumption is very low.DD process is also clean and easy to operate. So DD is a simple and effective and economical method to solve the problem of waste liquid. In addition, in recent years, many special separation fields need to be satisfied. For example, the process of seawater desalination often hopes the ion exchange membrane can be used. Selective separation of valence ions and separation of specific ions from complex water and salt solutions. Electrodialysis (ED) is a process of migration of ions through ion exchange membranes under the action of direct current electric field. It has the characteristics of low energy consumption, easy operation, long service life and no pollution. In the process of ED, the selective permeable membrane is selected for different valence states. The transfer properties of ions are different and thus make them separate. Therefore, the preparation of the corresponding selective ion exchange membrane is of great significance for the separation of one or two valence ions by electrodialysis. The common atom transfer radical polymerization (ATRP) and the atom transfer free radical polymerization (ARGET-ATRP) of the electron transfer activation regeneration catalyst have developed rapidly in recent years. The method of active polymerization, which is of important value, can not only control the molecular weight of the polymer and the polydispersity of the polymer chain, but also control the composition of the polymer, the structure and the functional group of the end group. In this way, the block and graft copolymers of the predetermined structure and sequence can be prepared. This paper includes five Chapter 1 is the introduction, which is divided into two parts. The first part introduces the hazards and conventional treatment methods of industrial waste liquid, diffusion dialysis (DD) method, device and ATRP, ARGET-ATRP. second, introduces the application value, preparation method and electrodialysis (ED) of the one or two valence ion selective membrane. The second chapter explores through several ATRP parties Sodium polystyrene sulfonate (PSSS) was prepared by the method, including the polymerization of sodium phenylene sulfonate (SSS) by 2- bromide ethyl (EBiB) by common ATRP method, and PPO-CH2Br as a large molecular initiator with brominated poly (2,6- two methyl -1,4- phenyl ether) (BPPO). IB leads to SSS for ARGET ATRP polymerization. The first two methods have some shortcomings, the third methods can successfully prepare polyelectrolyte (PSSS). In the third chapter, polyelectrolyte (PSSS) and polyvinyl alcohol (PVA) are blended and crosslinked with silane coupling agent, after coating the film and heat treatment to get the cation exchange membrane. We are from water content, 65 C water. The properties of the membrane are characterized by swelling properties and ion exchange capacity (IEC), and they are applied to the diffusion dialysis (DD) process to treat the simulated industrial wastewater (NaOH/Na2WO4) system. The hydrophilic property of the PVA matrix in the membrane is stronger and can provide a large number of hydroxyl groups (-OH), and the permeability of the hydrated ions, such as OH- is higher, and the PSSS component contains a large amount of ion exchange. In the fourth chapter, the fourth chapter describes the grafting of SSS on the commercial brominated poly (2,6- two methyl -1,4- phenyl ether) (BPPO) membrane through the SI-ATRP method and the quaternification of the BPPO matrix. The main body of the membrane is the main body of the membrane. A large number of positive charges (-N+ (CH3) 3) and a layer of negative charge (-S03-) are grafted on the surface. We characterize the membrane from water content, ion exchange capacity (IEC), thermal stability, ion migration number and so on. The separation and selection performance of the membrane to one or two valence anions is investigated by conducting electrodialysis (ED) on the NaCl/Na2SO4 system. The fifth chapter is the full text The analysis and summary on how to prepare ion exchange membrane by ATRP method and the application prospect of this kind of membrane in DD and ED are analyzed and summarized, and some meaningful conclusions are drawn.
【學位授予單位】:合肥工業(yè)大學
【學位級別】:碩士
【學位授予年份】:2015
【分類號】:TQ028.7

【參考文獻】

相關(guān)期刊論文 前2條

1 李博;劉述平;唐湘平;;銅鉛鋅多金屬共生礦濕法冶金研究進展[J];礦產(chǎn)綜合利用;2010年06期

2 羅愛平,王曉春,劉軍,張啟修;離子交換膜擴散滲析分離堿鎢的可行性研究[J];五邑大學學報(自然科學版);2000年02期



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