【作者】 陈敏；

【导师】 戴起勋；

【作者基本信息】 江苏大学 ， 材料学， 2007， 博士

【摘要】 芳香族聚合物由于具有热稳定性高、化学稳定性好、质地轻且牢固以及良好的加工成型性等优点,受到人们的日益重视。然而其推广应用受到多环芳烃单体制备困难的限制。由芳香族化合物的选择性酰基化、烷基化及偶联等反应,可得到主链型芳香族高分子的中间体,这是功能高分子材料的重要研究方向。较之单环芳烃,多环芳烃中间体电子云密度更高,相应的聚合物热稳定性、化学稳定性更好、质地更为牢固。但目前对芳烃的Friedel-Crafts酰基化、Friedel-Crafts烷基化和偶联等反应的研究主要集中在苯环和萘环,更多环芳香族的研究则显得很薄弱。本研究首次研究了不同催化剂（金属卤化物、离子液体、杂多酸等）作用下,多环芳烃蒽的Friedel-Crafts酰基化、Friedel-Crafts烷基化反应和苊的偶联反应,得到1,2-蒽乙二酮、9-苯甲酰蒽、2-异丙蒽和3,3’-联苊等多种新型多环芳烃功能高分子中间体。根据各因素对反应的影响结果,蒽、苊及催化剂的结构特点,并结合GC/MS、FT-IR和¹H NMR谱图分析,探讨了上述各反应的反应机理,合理解释了几种新型多环芳烃高分子中间体的生成,取得了如下结果:1)以[Bmim]Cl-AlCl₃离子液体为催化剂和溶剂,利用蒽与草酰氯的Friedel-Crafts酰基化反应,在温和条件下成功合成了新型功能高分子中间体1,2-蒽乙二酮,用萃取、重结晶等方法得到了1,2-蒽乙二酮纯品,对其用GC、GC/MS、FT-IR和¹H NMR等分析测试手段确认了其结构;根据GC测试结果考察了不同反应条件对1,2-蒽乙二酮产率和选择性的影响,当AlCl₃在[Bmim]Cl-AlCl₃离子液体中的摩尔分数为0.67,n{[Bmim]Cl-AlCl₃}:n（蒽）=2∶1,n（草酰氯）:n（蒽）=2∶1,反应温度45℃,反应时间6h时,1,2-蒽乙二酮收率为88.2%,选择性可达98.2%;离子液体表现出了其突出的优势,催化活性高、具有催化剂和溶剂的双重功能、可以重复使用及环境友好等;根据不同反应条件对蒽与草酰氯的Friedel-Craft酰基化的影响,以及蒽和[Bmim]Cl-AlCl₃离子液体的结构特点,探讨了在[Bmim]Cl-AlCl₃离子液体催化作用下,蒽与草酰氯Friedel-Craf酰基化反应的机理,反应属于由草酰氯与离子液体相互作用产生的酰基正离子作为亲电试剂与蒽发生的亲电取代反应机理。2)用杂多酸型催化剂钨酸铝(AlPW₁₂O₄₀)催化了蒽和苯甲酰氯的Friedel-Craft酰基化反应,合成了功能高分子中间体9-苯甲酰蒽,提纯得到其纯品,用GC/MS、FT-IR和¹H NMR等分析测试结果确认了其结构;考察了各种反应条件对9-苯甲酰蒽收率和选择性的影响,得到9-苯甲酰蒽的优化合成条件为:反应温度90℃,反应时间为5h,n（蒽）:n（苯甲酰氯）:1.0∶1.5,催化剂百分含量为4.5%,溶剂为环己烷。上述条件下,9-苯甲酰蒽的收率和选择性分别可以达到47.4%和91.8%;实验结果表明,AlPW₁₂O₄₀具有对目标产物选择性高、无环境污染且可以回收利用等优点;根据实验结果探讨了杂多酸型磷催化剂钨酸铝催化蒽与苯甲酰氯的Friedel-Craf酰基化的反应机理,通过电子云密度、空间位阻等因素的讨论,对9-苯甲酰蒽的合成做了科学的解释。3)研究了无水AlCl₃、[Bmim]Cl-AlCl₃离子液体或AlPW₁₂O₄₀催化蒽与2-氯丙烷的Friedel-Craf烷基化反应。温和条件下,合成了高分子中间体2-异丙蒽,萃取、重结晶得到其纯品,GC/MS、FT-IR和¹H NMR等分析测试结果确认了其结构;实验研究了各催化剂作用下的优化反应条件,离子液体的催化效果最好,[Bmim]Cl-AlCl₃催化的优化反应条件下,2-异丙蒽收率和选择性分别为69.2%和为77.1%;对在无水AlCl₃、[Bmim]Cl-AlCl₃离子液体及AlPW₁₂O₄₀催化下,蒽与氯代异丙烷Friedel-Craf烷基化反应制备2-异丙蒽,分别从反应热力学控制与动力学控制等方面对2-异丙蒽的亲电取代机理进行了讨论。4)分别研究了在BF₃、AlCl₃、FeCl₃等常用无机盐Lewis酸和[Bmim]Cl-AlCl₃、[Bmim]Cl-FeCl₃离子液体催化作用下,苊在温和条件或微波下的偶联反应。实验成功合成了功能高分子中间体3,3’-联苊,并利用旋转蒸发、薄层层析、重结晶等多种提纯方法得到3,3’-联苊纯品。根据提纯物的GC/MS、FT-IR、¹H NMR等谱图确定了其结构。研究了各种催化剂作用下合成3,3’-联苊的最佳反应条件,比较了各类催化剂对3,3’-联苊合成的催化活性的高低。结果表明,[Bmin]Cl-FeCl₃离子液体对3,3’-联苊合成的催化效果最好,在其催化的最佳反应条件下,3,3’-联苊收率为38.5%,选择性达99.1%;利用加入自由基猝灭剂的方法和对反应产物的GC/MS、FT-IR、¹H NMR等谱图分析探讨了各催化剂作用下苊的偶联反应的机理,苊在BF₃·OEt₂和AlCl₃催化作用下的偶联反应,属典型的自由基机理,根据自由基中间的稳定性及链反应的特征,合理解释了3,3’-联苊的生成。而FeCl₃及[Bmin]Cl-AlCl₃和[Bmin]Cl-FeCl₃离子液体催化的苊偶联反应是通过碳正离子历程催化苊得到3,3’-联苊。更多还原

【Abstract】 In recent years,aromatic polymers are now invoking more and more interests because of their many advantages,such as good thermal and chemical stabilities,low density but robustness and facility to process,but their wider application is limited by the preparation of aromatic monomers（i.e,macromolecule intermediate）.Such macromolecule intermediates can be synthesized by selective acylation,alkylation or coupling of aromatics,which is an important research direction of functional macromolecule intermaterials.So far,the studies of Friedel-Craft acylation,Friedel-Craft alkylation or coupling of aromatics are mainly focused on benzene and naphthalene or their ramifications,while few reports have been found in the literatures on the researchs of polycyclic aromatic hydrocarbons.In the present dissertation,the Friedel-Craft acylation and Friedel-Craft alkylation of anthracene and the coupling of acenaphthene catalysed by different catalysts（metal halid,ionic liquids and heteropoly acid）were firstly investigated.Several new functional macromolecule intermediates such as 1,2-aceanthrylenedione,9-Benzoylanthracene, 2-isopropylanthracene and 3,3’-biacenaphthene were selectively synthesized.The mechanisms of above reactions were explored by corresponding experimental results,the structure characteristics of anthracene,acenaphthene and catalysts as well as analysis of MS,FT-IR and ¹H NMR.Thus,reasonable analysises of all reaction products were realized.Some significant results are as follows:1)[Bmim]Cl-AlCl₃ ionic liquid was used as catalyst and solvent in the Friedel-Crafts acylation of anthracene with oxalyl chloride to synthesize the new functional macromolecule intermediates 1,2-aceanthrylenedione, Pure 1,2-aceanthrylenedione was prepared by extraction and recrystalling and the structure of 1,2-aceanthrylenedione was identified by GC/MS, FT-IR and ¹H NMR analysis.The effects of various reaction comditions on the the yield and selectivity of 1,2-aceanthrylenedione were studied by GC analysis.The results showed that the optimum synthesis conditions of the acylation reaction are as follow:the molar fraction of AlCl₃ in [Bmim]Cl-AlCl₃ being 0.67,n{[Bmim]Cl-AlCl₃}:n（anthracene）=2:1, n（oxalyl chloride）:n（anthracene）= 2:1,the reaction temperature 45℃and the reaction time 6 h.Under those conditions,the yield of 1,2-aceanthrylenedione is 88.2%and selectivity is 98.2%.Farther more, [Bmim]Cl-AlCl₃ ionic liquid not only shows excellent catalysis activity, dual role as catalyst and solvent,but also can be reuse and has little pollution to environment.The mechanism of the Friedel-Craft acylation of anthracene with oxalyl chloride in the presence of[Bmim]Cl-AlCl₃ was explored by examining effects of various reaction conditions on the yield and selectivity of 1,2-aceanthrylenedione and the structure characteristic of anthracene as well as[Bmim]Cl-AlCl₃ Ionic Liquid.The results show that acylium cation as electrophilic reagent produced by oxalyl chloride interaction with[Bmim]Cl-AlCl₃ ionic liquid attack anthracene.It is belong to electrophilic substitution mechanism.2)The Friedel-Craft acylation of anthracene with oxalyl chloride catalysed by AlPW₁₂O₄₀heteropolyacid was studied.9-Benzoylanthracene was determined by GC/MS analysis and pure 9-benzoylanthracene was prepared.The structure of 9-benzoylanthracene was confirmed by GC/MS,FT-IR and ¹H NMR,and the effects of various reaction comditions on the the yield and selectivity of 9-benzoylanthracene was studied.The results showed that the most suitable synthesis conditions are solvent cyclohexane,n（benzoyl chloride）:n（anthracene）= 2:1,catalyst mass fraction 4.5%,reaction temperature 90℃and reaction time 5 hour.Under those conditions,the yield of 9-benzoylanthracene is 47.4%and the selectivity towardes 9-benzoylanthracene is 91.8%.Additionally, AlPW₁₂O₄₀has no pollution to environment and can be easily recovered after the reaction for reused.Preparation of 9-benzoylanthracene was scientific discussed by studying the mechanism of the Friedel-Craft acylation of anthracene with oxalyl chloride catalysed by AlPW₁₂O₄₀ through analyzing the density of electron cloud and interspace obstacle of anthracene,characteristic of AlPW₁₂O₄₀and experimental results.3)The Friedel-Craft acylation of anthracene with oxalyl chloride catalysed by anhydrous AlCl₃,[Bmim]Cl-AlCl₃ ionic liquid and AlPW₁₂O₄₀heteropolyacid was studied.2-isopropylanthracene,which was used as new macromolecule intermediate was determined by GC/MS. Pure 2-isopropylanthracene was obtained by extraction and recrystalling the reaction mixture and its strcture was determined through GC/MS, FT-IR and ¹H NMR.Optimum synthesis conditions were gained by examining the effects of various reaction comditions on the yield and selectivity of 2-isopropylanthracene.Among the three catalysts, [Bmim]Cl-AlCl₃ ionic liquid has the highest catalysis activity on the Friedel-Craft acylation of anthracene with oxalyl chloride.Under the optimum reaction conditions catalysed by[Bmim]Cl-AlCl₃,yield and selectivity of 2-isopropylanthracene is 47.4%and 91.8%.The reaction mechanisms of the preparation of 2-isopropylanthracene were explained with electrophilic substitution,which was discussed from the aspect of thermodynamics control and kinetics control,erespectively.4)The coupling reaction of acenaphthene catalyzed by Lewis acids （AlCl₃,FeCl₃,BF₃-OEt₂）and ionic liquids（[Bmim]Cl-AlCl₃,[Bmim]Cl-FeCl₃） were investigated at room temperature,ambient atmosphere or under microwave radiation.3,3’-biacenaphthenyls,which canbe used as new intermediate of function aromatic polymer material,was successfully synthesized.Pure 3,3’-biacenaphthenyls was purified by rotary evaporation,recrystallization and chromatography,and its structure was characterized by GC /MS,FT-IR,¹H NMR.The optimun reaction conditions were studied and the catalysis activity of different catalysts were compared.The results showed that[Bmim]Cl-FeCl₃ ionic liquid is the best effective catalysis among above of them on the preparation of 3,3’-biacenaphthenyls and under the optimum reaction conditions catalysed by[Bmim]Cl-FeCl₃,the yield of 3,3’- biacenaphthenyls is 38.5%and the selectivity towardes 3,3’- biacenaphthenyls is 99.1%.The mechanism of coupling reaction was discussed through the method of adding free radical scavenger and the analysis of MS,FTIR and ¹H NMR.The resuts suggest that the coupling reaction catalyzed by AlCl₃ and BF₃·OEt₂ are belong to typical free radical mechanism,while those of catalyzed by FeCl₃, [Bmin]Cl-AlCl₃ and[Bmin]Cl-FeCl₃ are proceed along carbonium mechanism to produce 3,3’-biacenaphthenyls.更多还原