本文選題：氟烷基化反應(yīng)　切入點(diǎn)：異雙官能團(tuán)氟烷基化試劑　出處：《中國科學(xué)技術(shù)大學(xué)》2017年博士論文

【摘要】：自1896年氟代乙酸乙酯的合成以來,有機(jī)氟化學(xué)(包括含氟高分子化學(xué))作為有機(jī)化學(xué)的一個重要的分支領(lǐng)域,一直表現(xiàn)出蓬勃的發(fā)展趨勢。由于氟原子具有電負(fù)性強(qiáng),極化率低和原子半徑較小等特點(diǎn),氟原子的引入會導(dǎo)致化合物產(chǎn)生獨(dú)特的物理、化學(xué)及生物性質(zhì),因此在眾多高端科技(核能、航天、半導(dǎo)體等)及重大工業(yè)(氯堿工業(yè)和新能源項目等)和醫(yī)藥、農(nóng)藥等領(lǐng)域都對含氟化合物有著廣泛且深入的研究和應(yīng)用。由于自然界中幾乎不存在天然的含氟有機(jī)化合物,因此通過人工化學(xué)合成是獲得含氟有機(jī)化合物的主要方法。近二十年來,人們致力于研究氟化和氟烷基化的新型方法,多種多樣的含氟化合物和材料相繼被制備出來,并且其中眾多化合物已經(jīng)成功地應(yīng)用于醫(yī)藥化合物和工程材料領(lǐng)域。但是隨著生物醫(yī)學(xué)研究和先進(jìn)高科技材料的發(fā)展,探索新型的含氟有機(jī)化合物和高分子材料已經(jīng)成為有機(jī)氟化學(xué)領(lǐng)域重要的發(fā)展方向。本論文從烯烴的雙功能化反應(yīng)和含氟聚合物的制備兩個角度出發(fā),以三氟氯乙烯為原料,制備出了多種新型含氟烷基化合物和含氟高分子材料,包括氟烷基化試劑、氟烷基硫化試劑、氟磺酸聚合物膜和含氟可降解聚合物等。主要的研究內(nèi)容和成果分為以下四個部分:1.通過三氟氯乙烯與疊氮化鈉和氯化碘的三組分反應(yīng),制備出一種新型氟烷基化試劑,1-疊氮基-2-氯-1,1,2-三氟-碘乙烷(ACTI)。作為一種異雙官能團(tuán)氟烷基化試劑,兩端分別為高反應(yīng)活性的疊氮基團(tuán)和氟烷基碘基團(tuán)。在CuI和TBAA組成的催化劑下,實現(xiàn)了與芳基或烷基炔的"點(diǎn)擊化學(xué)"反應(yīng),并且獲得較高的產(chǎn)率。同時,我們對反應(yīng)機(jī)理進(jìn)行了詳細(xì)地探究。實驗結(jié)果表明,TBAA不僅僅是作為CuI的配體,而且其醋酸根離子在催化反應(yīng)進(jìn)行的過程中起到關(guān)鍵作用。此外,生成物中的氟烷基碘官能團(tuán),與普通氟烷基碘相同的化學(xué)性質(zhì),可以實現(xiàn)一些自由基化學(xué)和光化學(xué)的特征性反應(yīng),從而合成各種具有不對稱結(jié)構(gòu)的含氟有機(jī)化合物。2.系統(tǒng)研究了疊氮化鈉、三氟氯乙烯和2-硫氰基嘧啶的三組分化學(xué)反應(yīng)的條件,首次制備出一種新型的氟烷基化試劑基試劑,2-((2-疊氮-1-氯-1,2,2-三氟乙基)硫醚)嘧啶(ACTP)。作為一種異雙官能團(tuán)氟烷基試劑,其一端是氟烷基疊氮基團(tuán),另一端是氟烷基嘧啶硫醚基團(tuán)。我們詳細(xì)地考察了這兩種功能性基團(tuán)的反應(yīng)特征及拓展反應(yīng)。研究結(jié)果表明,ACTP是一種多功能性的氟烷基化試劑,一方面,在CuI/TBAA的催化體系卜下,疊氮基團(tuán)可以成功地與炔基化合物實現(xiàn)"點(diǎn)擊化學(xué)'反應(yīng);另一方面,氟烷基嘧啶基團(tuán)可以被氧化成嘧啶砜基團(tuán),并且且通過進(jìn)一步的還原脫除和氧化反應(yīng),轉(zhuǎn)換成亞磺酸鈉和磺酸鈉官能團(tuán)。最后,利用這種新型的異雙官能團(tuán)含硫氟烷基試劑,成功的將氟磺酸基團(tuán)引入到高分子側(cè)基中,制備出一種新型的含氟磺酸質(zhì)子交換膜材料,并且具有一定的質(zhì)子傳導(dǎo)性能。3.合成多種RAFT試劑(三硫代酯、二硫代酯和氨基甲酸酯等),分別考察其對于熱引發(fā)三氟氯乙烯和乙烯基丁醚自由基共聚合的控制性,結(jié)果發(fā)現(xiàn)乙氧基對三氟甲基芐基二硫代甲酸酯表現(xiàn)出最佳的控制性。通過分子量分布和反應(yīng)動力學(xué)的研究,證明該聚合過程具有"活性/可控"的特征。利用1H、19F和13C NMR譜確認(rèn)了三氟氯乙烯與乙烯基丁醚在自由基聚合條件下形成了交替結(jié)構(gòu)。不過,MALDI-TOF-MS測試和絕對分子量的計算的結(jié)果表明,共聚物中存在三氟氯乙烯頭尾加成的均聚單元結(jié)構(gòu),這說明三氟氯乙烯和乙烯基丁醚的交替共聚是基于交叉鏈增長的機(jī)理,而不是基于單體對電荷轉(zhuǎn)移絡(luò)合物的機(jī)理。對不同轉(zhuǎn)化率下1HNMR積分計算和小分子的模擬反應(yīng),推測出在聚合中氟烷基自由基難于與二硫代酯化合物進(jìn)行可逆加成斷裂鏈轉(zhuǎn)移反應(yīng),自由基優(yōu)先與乙烯基醚單體反應(yīng),生成的乙基丁基醚自由基再向二硫酯可逆加成斷裂鏈轉(zhuǎn)移,從而實現(xiàn)可控/活性自由基聚合。最后,通過乙烯基自縮合(SCVP)的方法,成功制備出一種基于三氟氯乙烯和乙烯基丁醚的含氟支化聚合物。4.5,6-苯并-2-亞甲基-1.3-二氧環(huán)庚烷(BMDO)是一種常見的自由基開環(huán)聚合單體,廣泛的應(yīng)用于各種含酯鍵高分子材料的合成。我們以過氧化月桂酰(LPO)為自由基引發(fā)劑,成功的實現(xiàn)了 BMDO和三氟氯乙烯以及乙烯基丁醚的三元和二元自由基共聚合。共聚物的結(jié)構(gòu)和組成通過1HNMR、13CNMR、19F NMR、FT-IR和元素分析進(jìn)行了表征。實驗結(jié)果表明,三氟氯乙烯和BMDO、乙烯基丁醚都傾向于交替共聚合,共聚物中三氟氯乙烯的單元的含量幾乎保持50%不變;在不同的BMDO和乙烯基丁醚的初始投料比下,所得共聚物中,BMDO和乙烯基丁醚含量比高于投料比。共聚物的熱性能與BMDO含量有關(guān),熱穩(wěn)定性隨BMDO單元含量的增加而下降。此外,這種含氟共聚合物可以發(fā)生水解反應(yīng),結(jié)果表明它具有較好的化學(xué)降解性能。
[Abstract]:Since the synthesis of fluoro ethyl acetate since 1896, organic fluorine chemistry (including fluorinated polymer chemistry) as an important branch in the field of organic chemistry, has shown a booming trend. Due to the electronegativity of the fluorine atom has strong characteristics of low and small radius of atomic polarizability, the introduction of fluorine atoms will lead to compounds have unique physical, chemical and biological properties, so in many high-end technology (nuclear, aerospace, semiconductor, etc.) and major industrial (chlor alkali industry and new energy projects) and pharmaceutical, pesticide and other fields have a broad and in-depth research and application of fluorine-containing compounds. Because the nature is almost non-existent fluorine containing natural organic compounds, so the artificial chemical synthesis is the main method of fluorinated organic compounds. In the past twenty years, people devote to study new methods of fluoride and fluoroalkylation, variety Fluorine containing compounds and materials have been successfully fabricated, and many compounds have been successfully applied in the fields of medicine and compound engineering materials. But with the development of biomedical research and advanced high-tech materials, exploring new fluorinated organic compounds and polymer materials has become an important development direction in the field of organic fluorine chemistry. In this thesis, two functional reaction of olefins and preparation of fluoropolymer with two angles, with three fluoride vinyl chloride as raw materials, preparation of a variety of novel fluorinated alkyl compounds and fluorinated polymer materials, including fluoroalkylation reagent, fluoroalkyl sulfide reagent, perfluorinated sulfonic acid polymer film and fluorinated biodegradable polymers the main research contents and achievements are divided into the following four parts: 1. through three fluoride vinyl chloride and sodium azide and iodine chloride three component reaction to prepare a new fluoroalkylation 1- reagent, azido -2- chloro -1,1,2- three fluorine iodine ethane (ACTI). As a hetero bifunctional fluoroalkylation reagent, respectively for the high activity of azide groups and fluoroalkyl groups. Iodine catalyst composition in CuI and TBAA, achieved with aryl or alkyl alkynyl "click on the" chemical reaction, and high yield. At the same time, we carried out a detailed study on the reaction mechanism. The experimental results show that TBAA is not only as the ligand of CuI, and the acetate ion in the catalytic reaction plays a key role. In addition, fluoroalkyl iodides in chemical functional groups generated. The nature and the same as ordinary fluoroalkyl iodide, can realize the characteristic reaction of some free radical chemistry and photochemistry, asymmetric structure of.2. containing organic compounds in the system of sodium azide and fluoride synthesis with three fluorine, vinyl chloride and sulfur cyanopyrimidine 2- 鐨勪笁緇勫垎鍖栧鍙嶅簲鐨勬潯浠，

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