【摘要】：作為一種新型的“綠色溶劑”和催化劑,離子液體有望代替?zhèn)鹘y(tǒng)的有機(jī)溶劑和有機(jī)催化劑,實(shí)現(xiàn)綠色化學(xué)中綠色原料、綠色催化劑的需要。離子液體起了重要的作用,某種意義上說,離子液體是濃縮的綠色化學(xué)的符號。離子液體具有如下優(yōu)異的物理化學(xué)性能:即使在真空下也難以察覺的蒸汽壓;在較大的溫度范圍內(nèi)仍呈現(xiàn)液態(tài);電化學(xué)窗口寬;熱穩(wěn)定性高等。盡管近年來對于離子液體的應(yīng)用方面的報(bào)道日益遞增,但對于其制備及純化卻比較少。離子液體合成方法主要分為一步法和兩步法。雖然一步法可以獲得高純度的離子液體,但是離子液體陰陽離子的種類會(huì)受到有限的烷基化試劑的限制,兩步法還是離子液體的主要合成方法。但是傳統(tǒng)兩步法面臨著諸多問題,例如收率低、合成時(shí)間長、反應(yīng)溫度高、雜質(zhì)含量高。本文設(shè)計(jì)新型的合成方法—氧化還原法制備了一系列季銨鹽離子液體,在含有目標(biāo)陰離子的質(zhì)子酸和1-己烯作為溴清除劑的情況下,使用雙氧水與季銨溴鹽反應(yīng)合成離子液體,合成了一系列以四甲基銨,四乙基銨和四正丁基銨為陽離子與以5種酸根CH3SO3-、HSO4-、NO3-、CF3COO-和TsO-為陰離子的室溫離子液體。合成的離子液體產(chǎn)品結(jié)構(gòu)經(jīng)過1H NMR和13C NMR表征確定為目標(biāo)產(chǎn)品,用離子色譜和卡爾費(fèi)休水份滴定儀分別測量了產(chǎn)品中的溴雜質(zhì)和水分含量。結(jié)果表明,在室溫條件下反應(yīng)3~4h,離子液體收率高達(dá)98%,溴雜質(zhì)含量和水分含量較低。該方法相比較于傳統(tǒng)的方法,不僅可以制備高純度和高收率的離子液體,而且簡化實(shí)驗(yàn)條件,具有反應(yīng)條件溫和,反應(yīng)時(shí)間短,產(chǎn)品收率和純度高的優(yōu)點(diǎn)。實(shí)驗(yàn)同時(shí)證明,含有雙鍵官能團(tuán)的離子液體和弱酸型離子液體不適合氧化還原法合成。
[Abstract]:As a new type of "green solvent" and catalyst, ionic liquids are expected to replace the traditional organic solvents and organic catalysts to meet the needs of green raw materials and catalysts in green chemistry. Ionic liquids play an important role. In a sense, ionic liquids are symbols of concentrated green chemistry. Ionic liquids have the following excellent physical and chemical properties: vapor pressure, which is difficult to detect even in vacuum; liquid state in large temperature range; wide electrochemical window; high thermal stability. Although the application of ionic liquids has been increasing in recent years, the preparation and purification of ionic liquids are relatively rare. The synthetic method of ionic liquid is mainly divided into one step method and two step method. Although high purity ionic liquids can be obtained by one step method, the species of anions and anions of ionic liquids will be limited by limited alkylation reagents, and the two-step method is still the main method for the synthesis of ionic liquids. However, the traditional two-step method is faced with many problems, such as low yield, long synthesis time, high reaction temperature and high impurity content. A series of quaternary ammonium salt ionic liquids were prepared by redox method. Ionic liquids were synthesized by the reaction of hydrogen peroxide with quaternary ammonium bromide with protonic acid and 1-hexene containing target anions as bromine scavengers. A series of room temperature ionic liquids with tetramethylammonium tetraethylammonium and tetra-Ding Ji ammonium as cations and CH3SO3-,HSO4-,NO3-,CF3COO- and TsO- as anions were synthesized. The synthesized ionic liquid product was characterized by 1H NMR and 13C NMR. The bromine impurity and water content in the product were measured by ion chromatography and Karl Fischer water titration apparatus. The results showed that the yield of ionic liquid was up to 98% at room temperature for 3 h, and the content of bromine impurity and water was lower. Compared with the traditional method, this method can not only prepare ionic liquids with high purity and high yield, but also simplify the experimental conditions. It has the advantages of mild reaction conditions, short reaction time, high yield and high purity. At the same time, it is proved that ionic liquids containing double bond functional groups and weak acid ionic liquids are not suitable for redox synthesis.
【學(xué)位授予單位】：沈陽化工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O645.1

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 陳慧,戴立益,單永奎,何鳴元;新型離子液體體系催化苯與1-己烯的烷基化反應(yīng)[J];應(yīng)用化學(xué);2003年09期

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本文編號：2287250