本文選題：離子液體聚合物 + 聚集行為　； 參考：《浙江理工大學(xué)》2017年碩士論文

【摘要】：離子液體聚合物(PILs)保留了離子液體的結(jié)構(gòu)特性,具有自發(fā)聚集能力,但與小分子的離子液體(ILs)相比,PILs在溶液中的運(yùn)動過程受到的影響更多,組裝過程也更為復(fù)雜。PILs有序體的構(gòu)建多數(shù)采用先單體有序組裝,然后聚合鎖定的方法進(jìn)行,但聚合過程中單體有序結(jié)構(gòu)被破壞是其進(jìn)一步應(yīng)用的瓶頸。此外,PILs有序體的結(jié)構(gòu)設(shè)計和其功能性材料性能的優(yōu)化是近些年的研究熱點(diǎn),但對于PILs分子鏈如何自發(fā)地進(jìn)行有序聚集,尤其是其聚集過程的熱力學(xué)行為很少見報道。基于此,本文首先采用自由基聚合的方法制備PILs,然后將PILs溶于溶劑,系統(tǒng)探究PILs在溶液中的自發(fā)聚集過程及相關(guān)的影響因素。另外,利用該方法所制備的PILs在PH響應(yīng)、抑菌材料方面的應(yīng)用還需要進(jìn)行進(jìn)一步評價。本文合成咪唑類離子液體聚合物poly[C_nVIm~+][X~-](n=8,12,16)(X為配對離子),利用烷基鏈和陰離子的結(jié)構(gòu)可設(shè)計性,探究其在有機(jī)溶劑中的聚集行為、刺激響應(yīng)性和抗菌功能上應(yīng)用。論文主要結(jié)論如下:(1)利用自由基聚合合成不同烷基鏈長的咪唑類離子液體聚合物,poly[CnVI m+][Br~-](n=8,12,16),其在正丙醇中可以自發(fā)聚集成有序結(jié)構(gòu),當(dāng)烷基鏈為16時,其在正丙醇中的聚集形態(tài)為多層“洋蔥狀”結(jié)構(gòu),這種“洋蔥狀”形貌與陰離子種類無關(guān),而且可以長時間保持。(2)通過電導(dǎo)率法對poly[C_nVIm~+][Br~-](n=8,12,16)在正丙醇的熱力學(xué)行為的進(jìn)行研究。結(jié)果表明,PILs在正丙醇中的聚集過程是熵驅(qū)動的自發(fā)過程。隨著烷基鏈的增加,臨界聚集濃度(CAC)降低,每條烷基鏈對吉布斯自由能(?G_m~θalkyl)的貢獻(xiàn)增加,聚集過程是在疏水作用下完成聚集過程。當(dāng)向體系中加入不良溶劑時,CAC和吉布斯自由能(?G_m~θ)隨著不良溶劑體積分?jǐn)?shù)的增加而降低,自發(fā)聚集行為更容易進(jìn)行。(3)通過陰離子交換實(shí)驗將poly[C_nVIm~+][Br~-](n=8,12,16)引入具有pH響應(yīng)的陰離子(Mo~-),功能化后的PILs表現(xiàn)出優(yōu)異的pH響應(yīng)性。隨著pH的增加,PILs溶液顏色由紅色變成黃色,其聚集尺寸隨著pH的增加而明顯增大。具有高陰離子交換率的poly[C_nVIm~+][Br~-]x[Mo~-]y對酸堿響應(yīng)更為“靈敏”,同時,烷基鏈的增加使得PILs對酸堿響應(yīng)性變得“遲鈍”。(4)將聚合后的poly[C_nVIm~+][Br~-](n=8,12,16),通過透析的方式得到PILs膠束,研究PILs膠束對金黃色葡萄糖球菌(S.aureus)和大腸桿菌(E.coli)抗菌性能。不同烷基鏈長的PILs的臨界抑菌濃度(MIC)從低到高依次為:poly[C_(12)VIm~+][Br~-]poly[C_(16)VIm~+][Br~-]poly[C_8VIm~+][Br~-],并且poly[C_(12)VIm~+][Br~-]與細(xì)菌接觸1h后,細(xì)菌生存率幾乎為0。通過電荷屏蔽實(shí)驗研究了烷基鏈對抑菌的貢獻(xiàn),對于Poly[C_(12)VIm~+][Br~-]而言,烷基鏈對S.aureus抑菌的貢獻(xiàn)達(dá)到60%,對E.coli抑菌的貢獻(xiàn)達(dá)到67%。本文系統(tǒng)的研究了poly[C_nVIm~+][Br~-](n=8,12,16)在純?nèi)軇┖筒涣既軇┐嬖跅l件下的自發(fā)聚集過程和熱力學(xué)行為,考察了其在有機(jī)溶劑中的pH刺激響應(yīng)特性以及對金黃色葡萄糖球菌(S.aureus)和大腸桿菌(E.coli)抗菌性能。研究結(jié)果對于PILs功能材料的結(jié)構(gòu)設(shè)計和性能調(diào)控提供新思路。
[Abstract]:Ionic liquid polymers (PILs) retain the structural characteristics of ionic liquids and have the ability to assemble spontaneously, but compared with the ionic liquids (ILs) of small molecules, the movement process of PILs in the solution is more affected. The assembly process is also more complex for the construction of the complex.PILs ordered body by the ordered assembly of monomers, and then the method of polymerization locking. In addition, the structural design of the PILs ordered body and the optimization of its functional material performance are the hot spots in recent years. However, it is rare to report on how the PILs molecular chain is organized spontaneously and orderly, especially the thermodynamic behavior of its aggregation process. In this paper, we first prepare PILs by free radical polymerization, and then dissolve PILs in the solvent and systematically explore the spontaneous aggregation process of PILs in the solution and the related factors. In addition, the application of the PILs prepared by this method in PH response and the application of bacteriostasis materials need to be further evaluated. This paper syntheses imidazole ionic liquids. Polymer poly[C_nVIm~+][X~-] (n=8,12,16) (X is paired ion), using the structure of alkyl chains and anions to design, explore its aggregation behavior in organic solvents, stimulate responsiveness and antibacterial function. The main conclusions are as follows: (1) synthesis of imidazole ionic liquid polymers with different alkyl chain length by free radical polymerization, Po Ly[CnVI m+][Br~-] (n=8,12,16), in n-propanol, can be spontaneously integrated into an ordered structure. When the alkyl chain is 16, the aggregation morphology in n-propanol is a multilayer "onion like" structure, which is independent of the type of anions and can be maintained for a long time. (2) poly[C_nVIm~+][Br~-] (n=8,12,1) by conductivity method. 6) the thermodynamic behavior of n-propanol is studied. The results show that the aggregation process of PILs in n-propanol is a spontaneous process of entropy driven. With the increase of alkyl chain, the critical concentration (CAC) decreases, and the contribution of each alkyl chain to Gibbs free energy (? G_m~ theta alkyl) is increased, and the aggregation process is completed under the hydrophobic action. When the solvent is added to the system, the CAC and Gibbs free energy (? G_m~ theta) decreases with the increase of the volume fraction of the bad solvent, and the spontaneous aggregation behavior is easier. (3) the anion exchange experiment is used to introduce the poly[C_nVIm~+][Br~-] (n=8,12,16) into the pH response anion (Mo~-). The functional PILs shows excellent pH response. With the increase of pH, the color of PILs solution is yellow from red to yellow, and its aggregation size increases obviously with the increase of pH. The poly[C_nVIm~+][Br~-]x[Mo~-]y with high anion exchange rate is more "sensitive" to the acid base response. At the same time, the increase of alkyl chain makes PILs to be "dull" to the acid base response. (4) poly[C_nV after polymerization Im~+][Br~-] (n=8,12,16), PILs micelles were obtained by dialysis to study the antibacterial properties of PILs micelles to Staphylococcus aureus (S.aureus) and Escherichia coli (E.coli). The critical inhibitory concentration (MIC) of PILs with different alkyl chain length (MIC) from low to high was poly[C_ (12) VIm~+][Br~-]poly[C_ (16) VIm~+][Br~-]poly[C_8VIm~+][Br~-], and pol. After y[C_ (12) VIm~+][Br~-] was exposed to 1H with bacteria, the survival rate of bacteria was almost 0.. The contribution of alkyl chain to bacteriostasis was studied by the charge shielding experiment. For Poly[C_ (12) VIm~+][Br~-], the contribution of alkyl chain to S.aureus was 60%. The contribution of E.coli bacteriostasis to 67%. system was studied in poly[C_nVIm~+][Br~-] (n=8,12,16). The spontaneous aggregation process and thermodynamic behavior under the presence of pure solvent and bad solvent were used to investigate the response characteristics of pH stimulation in organic solvents and the antibacterial properties of Staphylococcus aureus (S.aureus) and Escherichia coli (E.coli) in organic solvents. The results provided new ideas for the structure design and performance regulation of PILs functional materials.

【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O631

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