芴的9位取代反应研究及其在菲和芴分离中的应用

It is of significance to investigate the 9-substituted reaction of fluorene for its further processing. This work is based on the structural modification of 9-C of fluorene, and there is a consistent thread running through the study of alkali metallization and acylation substituted reaction. The main contents are included the synthesis of fluorene formaldehyde, or fluorenealkali metal and the reduction of fluorene formaldehyde and the hydrolysis of fluorene alkali metal. Furthermore, the separation efficiency of phenathrene and fluorene in athracene residues by coupling the reaction-separation technique according the solubility difference between fluorene alkali metal /fluorene formaldehyde and phenathrene were investigated. The in-situ characterization techniques, such as electron spin resonance (ESR), attenuated total reflection flourier transformed infrared spectroscopy (ATR-FTIR) were applied to detect the intermediate product of fluorenyl carbonation. The relationship of the basicity of catalyst, the type and quality of the solvents and the additives with the formation of fluorenyl carbonation were determined to discover the common rules of the 9-substituted reaction of fluorene and to found the means of suppressing the bis-substituted reaction of fluorene carbonation. To Solve the low yields and selectivities of fluorene alkali metal and fluorene formaldyde, and oxidation reaction occurred during the reaction. Exploiting the new means to separate the phenathrene and fluorene from anthracene residues with highly efficience, and producing the high value-added chemical products meanwhile. And then lay the foundation of the unconventional separation of the complex materials. By the implement of this work, it is of great importance to instruct the synthesis of 9-substituted products of fluorene, to prolong the coking industry chain and to reuse the solid wastes as resource.

芴的9位取代反应研究对于芴的深加工利用具有重要意义。本项目以芴的9号位碳原子的结构修饰为基础，以芴的碱金属化/酰基化取代反应研究为主线，考察了芴甲醛合成及还原，芴碱金属盐制备及水解等过程，利用芴碱金属盐/芴甲醛与菲溶解性的差异，将反应-分离耦合技术用于蒽渣中菲和芴的分离过程。利用原位表征技术，顺磁共振、全反射红外光谱等对中间产物芴负离子进行检测，明确催化剂碱性、溶剂、助剂种类及用量等与芴负离子中间体形成的关系；揭示芴9位取代反应的一般规律；建立抑制芴负离子发生二次取代反应的方法。解决芴碱金属盐、芴甲醛制备过程产率低、选择性差，容易被氧化，以及芴甲醛还原制芴甲醇过程还原效率低等问题。开拓了蒽渣中菲和芴高效分离并联产高附加值下游化学品的新思路，为复杂样品的非常规分离研究奠定基础。该项目的实施对指导芴的9位取代产物合成、延长焦化产业链，固体废弃物的资源化利用都有重要意义。

蒽渣是高温煤焦油加工后的固体废弃物，富含菲、芴、咔唑和蒽等多环芳烃，均是重要的化工原料，因此，蒽渣提取菲、芴以及咔唑和蒽是其资源化利用的有效途径。由于菲与芴性质相近，采用常规方法很难实现有效分离。课题根据芴9位容易发生酰基化、羟甲基化、羧基化等取代反应的特点将芴转化为9-芴甲醛、9-芴甲酸、9-芴甲醇、9,9-双羟甲基芴等，而菲不转化的特点，采用反应–分离耦合技术，利用芴衍生物与菲溶解性的差异实现了蒽渣提取菲联产芴高附加值下游产品的目的。进而研究了蒽和咔唑的结晶分离过程。无论强碱还是弱碱性的碳酸盐均可以夺取芴9的亚甲基H得到芴负离子，进而发生亲核加成，通过加成–消除机理得到取代产物。以甲酸乙酯/甲酸正丁酯为酰基化试剂采用一段式温度实现了芴的快速酰基化，还原阶段以NaBH4–CaCl2为复合还原剂，不经溶剂转换，在碱水溶液中实现9-芴甲醛100%还原为9-芴甲醇。以芴与菲模型混合物为原料，经反应–分离后，菲的纯度为96.90％，收率为98.95％；9-芴甲醇纯度97.68％，收率最高可达91.58％。以蒽渣为原料，菲与9-芴甲醇的纯度分别为83.88％和94.35％，收率分别为64.46％和89.49％。以Cs2CO3为催化剂，实现了芴与CO2直接羧基化高选择性合成9-芴甲酸。以菲和芴模型混合物为原料，经两次反应后，芴几乎完全转化为9-芴甲酸，分离后9-芴甲酸和菲的纯度分别为96.55%和99.24%，收率分别为97.42%和92.46%。以K2CO3为催化剂，通过改变加料顺序和物料配比，实现了9-芴甲醇和9,9-双羟甲基芴的可控合成。产物为9-芴甲醇时，分离后9-芴甲醇的纯度为98.04%，收率为13.03%；产物为9,9-双羟甲基芴时，分离后菲纯度可达97.18%，收率98.96%。9,9-双羟甲基芴的纯度为87.26%，收率为73.87%。最后，通过考察溶剂、杂质、降温方式等对蒽和咔唑结晶过程的深入研究发现，溶液结晶过程中蒽–咔唑固溶体的形成是二者难以提纯的关键。课题开拓了有机固废资源化的新思路，为复杂样品的非常规分离奠定了基础。对蒽渣等复杂固废的资源化、减量化具有借鉴作用。