基于三氟氯乙烯的氟烷基试剂及聚合物的合成与表征

发布时间：2018-03-24 00:19

  本文选题：氟烷基化反应　切入点：异双官能团氟烷基化试剂　出处：《中国科学技术大学》2017年博士论文

【摘要】：自1896年氟代乙酸乙酯的合成以来,有机氟化学(包括含氟高分子化学)作为有机化学的一个重要的分支领域,一直表现出蓬勃的发展趋势。由于氟原子具有电负性强,极化率低和原子半径较小等特点,氟原子的引入会导致化合物产生独特的物理、化学及生物性质,因此在众多高端科技(核能、航天、半导体等)及重大工业(氯碱工业和新能源项目等)和医药、农药等领域都对含氟化合物有着广泛且深入的研究和应用。由于自然界中几乎不存在天然的含氟有机化合物,因此通过人工化学合成是获得含氟有机化合物的主要方法。近二十年来,人们致力于研究氟化和氟烷基化的新型方法,多种多样的含氟化合物和材料相继被制备出来,并且其中众多化合物已经成功地应用于医药化合物和工程材料领域。但是随着生物医学研究和先进高科技材料的发展,探索新型的含氟有机化合物和高分子材料已经成为有机氟化学领域重要的发展方向。本论文从烯烃的双功能化反应和含氟聚合物的制备两个角度出发,以三氟氯乙烯为原料,制备出了多种新型含氟烷基化合物和含氟高分子材料,包括氟烷基化试剂、氟烷基硫化试剂、氟磺酸聚合物膜和含氟可降解聚合物等。主要的研究内容和成果分为以下四个部分:1.通过三氟氯乙烯与叠氮化钠和氯化碘的三组分反应,制备出一种新型氟烷基化试剂,1-叠氮基-2-氯-1,1,2-三氟-碘乙烷(ACTI)。作为一种异双官能团氟烷基化试剂,两端分别为高反应活性的叠氮基团和氟烷基碘基团。在CuI和TBAA组成的催化剂下,实现了与芳基或烷基炔的"点击化学"反应,并且获得较高的产率。同时,我们对反应机理进行了详细地探究。实验结果表明,TBAA不仅仅是作为CuI的配体,而且其醋酸根离子在催化反应进行的过程中起到关键作用。此外,生成物中的氟烷基碘官能团,与普通氟烷基碘相同的化学性质,可以实现一些自由基化学和光化学的特征性反应,从而合成各种具有不对称结构的含氟有机化合物。2.系统研究了叠氮化钠、三氟氯乙烯和2-硫氰基嘧啶的三组分化学反应的条件,首次制备出一种新型的氟烷基化试剂基试剂,2-((2-叠氮-1-氯-1,2,2-三氟乙基)硫醚)嘧啶(ACTP)。作为一种异双官能团氟烷基试剂,其一端是氟烷基叠氮基团,另一端是氟烷基嘧啶硫醚基团。我们详细地考察了这两种功能性基团的反应特征及拓展反应。研究结果表明,ACTP是一种多功能性的氟烷基化试剂,一方面,在CuI/TBAA的催化体系卜下,叠氮基团可以成功地与炔基化合物实现"点击化学'反应;另一方面,氟烷基嘧啶基团可以被氧化成嘧啶砜基团,并且且通过进一步的还原脱除和氧化反应,转换成亚磺酸钠和磺酸钠官能团。最后,利用这种新型的异双官能团含硫氟烷基试剂,成功的将氟磺酸基团引入到高分子侧基中,制备出一种新型的含氟磺酸质子交换膜材料,并且具有一定的质子传导性能。3.合成多种RAFT试剂(三硫代酯、二硫代酯和氨基甲酸酯等),分别考察其对于热引发三氟氯乙烯和乙烯基丁醚自由基共聚合的控制性,结果发现乙氧基对三氟甲基苄基二硫代甲酸酯表现出最佳的控制性。通过分子量分布和反应动力学的研究,证明该聚合过程具有"活性/可控"的特征。利用1H、19F和13C NMR谱确认了三氟氯乙烯与乙烯基丁醚在自由基聚合条件下形成了交替结构。不过,MALDI-TOF-MS测试和绝对分子量的计算的结果表明,共聚物中存在三氟氯乙烯头尾加成的均聚单元结构,这说明三氟氯乙烯和乙烯基丁醚的交替共聚是基于交叉链增长的机理,而不是基于单体对电荷转移络合物的机理。对不同转化率下1HNMR积分计算和小分子的模拟反应,推测出在聚合中氟烷基自由基难于与二硫代酯化合物进行可逆加成断裂链转移反应,自由基优先与乙烯基醚单体反应,生成的乙基丁基醚自由基再向二硫酯可逆加成断裂链转移,从而实现可控/活性自由基聚合。最后,通过乙烯基自缩合(SCVP)的方法,成功制备出一种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-亚甲基-1.3-二氧环庚烷(BMDO)是一种常见的自由基开环聚合单体,广泛的应用于各种含酯键高分子材料的合成。我们以过氧化月桂酰(LPO)为自由基引发剂,成功的实现了 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。共聚物的结构和组成通过1HNMR、13CNMR、19F NMR、FT-IR和元素分析进行了表征。实验结果表明,三氟氯乙烯和BMDO、乙烯基丁醚都倾向于交替共聚合,共聚物中三氟氯乙烯的单元的含量几乎保持50%不变;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。共聚物的热性能与BMDO含量有关,热稳定性随BMDO单元含量的增加而下降。此外,这种含氟共聚合物可以发生水解反应,结果表明它具有较好的化学降解性能。
[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- 鐨勪笁缁勫垎鍖栧�﹀弽搴旂殑鏉′唬�

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