【摘要】：聚四氫呋喃是含兩個(gè)羥基官能團(tuán)的聚醚二醇,經(jīng)催化四氫呋喃單體聚合而成,分子呈線性結(jié)構(gòu)。平均分子量約2000的聚四氫呋喃主要用于合成氨綸的重要原料。聚四氫呋喃工業(yè)化生產(chǎn)工藝,常采用發(fā)煙硫酸、乙酸酐-高氯酸或氟磺酸作引發(fā)劑促使四氫呋喃發(fā)生聚合,但此類工藝存在腐蝕設(shè)備和后處理復(fù)雜等嚴(yán)重的后續(xù)處理問題。為了克服均相催化的缺限,研究者開始對(duì)聚合四氫呋喃的催化劑材料進(jìn)行深入探討。本文通過制備Nafion修飾炭基固體酸并進(jìn)行表征,研究其對(duì)四氫呋喃聚合的催化性能,揭示所制固體酸催化劑結(jié)構(gòu)、織構(gòu)及酸堿性等對(duì)材料催化四氫呋喃聚合的影響規(guī)律。本論文主要從以下兩個(gè)方面開展工作:(1)Nafion修飾葡萄糖炭基固體酸的制備及其催化THF聚合;(2)甲殼質(zhì)摻雜Nafion-炭基固體酸的制備及其催化THF聚合。圍繞以上兩方面,我們首先研究Nafion修飾葡萄糖炭基固體酸制備及催化THF聚合。探討不同Nafion含量,不同焙燒溫度對(duì)催化四氫呋喃聚合的影響。然后引入甲殼質(zhì)通過水熱合成法、模板法、浸漬法制備甲殼質(zhì)摻雜Nafion-炭基固體酸催化劑并探討其對(duì)THF聚合的催化作用。對(duì)所制的催化劑進(jìn)行表征:經(jīng)過X射線衍射(XRD)、紅外光譜(FT-IR)以及酸滴定法等得出結(jié)論,Nafion修飾葡萄糖炭基固體酸催化劑中具有磺酸基(-SO3H)且屬于無定形炭類型。當(dāng)Nafion溶液負(fù)載量增大時(shí),酸量增加,聚四氫呋喃的收率增高趨于平衡,相對(duì)分子量降低。而且溫度的升高也引起了酸量的減小,聚四氫呋喃收率增多而分子量下降。葡萄糖/殼粉用量的比例增多,聚四氫呋喃的收率增加,分子量增加。但前提是殼粉用量不大于葡萄糖用量。且加入殼粉比未加殼粉的催化劑對(duì)四氫呋喃聚合反應(yīng)具有更好的催化活性,聚合物的收率更高。得到結(jié)論甲殼質(zhì)是調(diào)節(jié)Nafion修飾葡萄糖炭基固體酸酸性的重要方法。
[Abstract]:Poly (tetrahydrofuran) is a polyether diol with two hydroxyl functional groups, which is synthesized by catalytic polymerization of tetrahydrofuran monomer. Polytetrahydrofuran with an average molecular weight of about 2000 is mainly used as an important raw material for the synthesis of spandex. In the industrial production process of polytetrahydrofuran, fuming sulfuric acid, acetic anhydride perchloric acid or fluorosulfonic acid are often used as initiators to promote the polymerization of tetrahydrofuran, but this process has serious problems such as corrosion equipment and complex post-treatment. In order to overcome the lack of homogeneous catalysis, researchers began to study the catalyst materials of polymerized tetrahydrofuran. In this paper, Nafion modified carbon-based solid acid was prepared and characterized to study its catalytic performance for tetrahydrofuran polymerization. The effects of structure, texture and acid-base of the solid acid catalyst on the catalytic activity of tetrahydrofuran polymerization were revealed. The main work of this thesis is as follows: (1) preparation of Nafion modified glucose carbon-based solid acid and its catalytic THF polymerization; (2) preparation of chitin doped Nafion- carbon-based solid acid and its catalytic THF polymerization. Around the above two aspects, we first studied the preparation of Nafion modified glucose carbon-based solid acid and its catalytic polymerization of THF. The effect of Nafion content and calcination temperature on the polymerization of tetrahydrofuran was studied. Then chitin was used to prepare chitin doped Nafion- carbon-based solid acid catalyst by hydrothermal synthesis template method and impregnation method and its catalytic effect on THF polymerization was discussed. The catalyst was characterized by X-ray diffraction (XRD), infrared spectroscopy (FT-IR) and acid titration. It was concluded that Nafion modified glucose carbon-based solid acid catalyst has sulfonic group (- SO3H) and belongs to amorphous carbon type. When the loading amount of Nafion solution increases, the acid content increases, the yield of polytetrahydrofuran tends to balance, and the relative molecular weight decreases. The increase of temperature also led to the decrease of acid content, the yield of polytetrahydrofuran increased and the molecular weight of polytetrahydrofuran decreased. The yield of polytetrahydrofuran increased and the molecular weight of polytetrahydrofuran increased with the increase of the ratio of glucose to shell powder. But the premise is that the amount of shell powder is no more than the amount of glucose. The addition of shell powder has better catalytic activity and the yield of polymer is higher than that of the catalyst without shell powder in the polymerization of tetrahydrofuran. Conclusion chitin is an important method to regulate the acidity of carboxylic acid modified by Nafion.
【學(xué)位授予單位】：山西大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;O633.5

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