【作者】 袁冰；

【导师】 程侣柏； 李宗石； 王桂茹；

【作者基本信息】 大连理工大学 ， 应用化学， 2006， 博士

【摘要】 芳酮类化合物种类繁多,应用广泛,在国民经济中占有举足轻重的地位。Friedel-Crafts酰基化反应是合成芳酮类化合物的最重要方法。目前,工业上通过Friedel-Crafts酰基化反应制备芳酮类化合物最常用的催化剂仍然是金属氯化物等均相酸催化剂,这类催化剂的大规模应用带来的环境、资源等问题越来越不能被环境友好的化学工业发展大趋势所容忍。因此,开发针对Friedel-Crafts酰基化反应的新型催化工艺,实现芳酮类化合物的绿色合成具有一定的应用价值和现实意义。本文以产物的工业应用价值为出发点,以H型沸石分子筛为催化剂,研究了三类芳酮的绿色化合成工艺。 分别采用AlCl₃和HZ-1沸石催化了β-甲基萘的Friedel-Crafts酰基化反应,合成了2,6-萘二甲酸的前体2-甲基-6-酰基萘。通过气相色谱、质谱及核磁共振技术对反应结果进行了分析,对目标产物的结构进行了表征。考察了沸石分子筛、萘环底物、酰化试剂、溶剂的种类等因素对酰化反应的影响,选定HZ-1沸石作为催化剂,丁酸酐作为酰化试剂,在无溶剂条件下催化β-甲基萘的酰化反应合成2-甲基-6-丁酰基萘。HZ-1沸石催化β-甲基萘的丁酰化反应副反应少,产品分离容易,2,6-位和2,7-位酰化产物异构体的熔点差异较大,便于工业上实现分离提纯。 研究了HZ-1沸石分子筛的焙烧温度、离子交换次数等制备条件对催化反应性能的影响,并通过NH₃-TPD、XRD、吡啶-IR、XRF等手段表征了制备条件对HZ-1沸石的硅铝比、结晶度及酸性质的影响,说明了催化性能随制备条件变化的原因。550℃焙烧的四次交换HZ-1沸石分子筛（HZ-1-4）表现出最佳的催化性能。考察了催化剂用量、物料配比、反应温度、反应时间等因素对β-甲基萘催化丁酰化反应的影响,优化了反应条件。在优化的反应条件下,反应中没有二酰化产物生成,也没有β-甲基萘的异构化以及歧化等副反应发生,反应产物仅为单丁酰化的各种异构体,以2,6-和2,7-位异构体为主。丁酸酐的转化率可达77.3%,2-甲基-6-丁酰基萘的选择性为53.1%。回收再用的HZ-1-4沸石的催化活性有较大幅度下降,经程序升温焙烧再生后,催化活性基本得以恢复。 考察了2%浸渍量的碱土金属、稀土金属、过渡金属氧化物改性后的HZ-1-4沸石对β-甲基萘的丁酰化反应的催化性能。改性后的HZ-1-4沸石催化活性有不同程度的下降,但选择性有所提高。综合考虑目标产物的收率和成本能耗问题,未改性的HZ-1-4沸石为β-甲基萘的丁酰化反应的最佳催化剂。 系统的研究了沸石分子筛催化带有不同取代基的芳环化合物的苯甲酰化反应。分别考察了HZ-1和HZ-2沸石催化剂对不同的苯环、萘环化合物的苯甲酰化性能,发现在更多还原

【Abstract】 Arones have been widely used as final products or intermediates in the field of dyes, Pharmaceuticals, agricultural chemicals and so on, and play an important role in the national economy. Friedel-Crafts acylation is the primary method for the preparation of arones, which involves the employment of metal chlorides as the homogeneous acid catalysts. Those environmentally unfriendly catalysts have always been an issue in the long-term application in industries. Therefore, the study of developing new catalysts for the Friedel-Crafts acylation to form arones becomes important and critical. In this research, H-type zeolite molecule sieves have been employed as catalysts to synthesize three types of arones, which have very important application in industries.2-methyl-6-acylnaphthalene, the precursor of 2, 6-naphthalic acid, has been synthesized via the Friedel-Crafts acylation of P-methylnaphthalene catalyzed by AICl₃ as well as HZ-1 zeolite and characterized by gas chromatography, mass spectrum and NMR techniques. Detailed studying on the effects of different zeolite molecule sieves, naphthalene ring substrates, acylating reagents and solvents on acylation has shown that the best condition is HZ-1 zeolite as catalyst, butytic anhydride as acylating reagent and no solvent involved. Under such conditions, the least side reactions have been processed. The biggish difference of melting points between 2-methyl-6-butyrylnaphthalene and 2-methyl-7-butyrylnaphthalene is propitious to the industrial separation.The influence of preparation conditions of HZ-1 zeolite such as calcined temperature and ion-exchanged times on the catalytic performance has been investigated. Besides, NH3-TPD, XRD, pyridine-IR and XRF have been employed to account for the change of SiO₂/Al₂O₃ ratio, crystallinity and acid properties of HZ-1 zeolite which will impact the catalytic performance. The four times exchanged HZ-1 zeolite calcined at 550°C exhibited optimal catalytic capability. The reaction conditions have also been optimized by adjusting catalyst dosage, reactants ratio, reaction temperature and reaction time. Under those optimized conditions, the conversion of butytic anhydride can reach as high as 77.3% with 53.1% selectivity for 2-methyl-6-butyrylnaphthalene without side-reaction occurred. Moreover, the catalytic activity of reused HZ-1 zeolite was found to decrease distinctly and can be resumed on the whole after regeneration.The catalytic performance of modified HZ-1-4 zeolite by 2% alkaline earth metal, raremetal and transition metal oxide in the butyrylation of P-methylnaphthalene has also been studied and the decrease of conversion and increase of selectivity were observed. Take both yield and cost into account, HZ-1-4 zeolite without modifiability should be chosen as the suitable catalyst in the Friedel-Crafts butyrylation of p-methylnaphthalene.In addition, benzoylation of aromatic compounds with different substituents in the presence of zeolite molecule sieves have been studied roundly. The catalytic performances of HZ-1 and HZ-2 zeolite in the benzoylation of different benzene ring as well as naphthalene ring compounds have been investigated. It has been found that the reaction activities of benzoylation are correlative with the activated degree of aromatics in the presence of zeolite molecule sieves, which correspond to the electrophilic aromatic substitution law.Several economically valuable benzophenones have been synthesized with higher yield by optimizing the benzoylation conditions of the different aromatics. HZ-1-4 zeolite has exhibited good catalytic performance in all the above benzoylation reactions. The yield of objective products 4-methoxylbenzophenone, 4-methylbenzophenone, 2-benzoylnaphthalene, 4-chlorobenzophenone and benzophenone can reach 93.8%, 94.8%, 86.0%, 76.0% and 58.0%, respectively, which are all higher than those in literatures.Magnified experiments of the benzoylation of toluene under the optimized reaction conditions have also been conducted for 4-methylbenzophenone over HZ-1-4 zeolite. Both catalyst and toluene can be recycled in such simple craft, and the distilled yield of 4-methylbenzophenone can reach 92.3% with a purity of 97.5% and good shape and colour. The total separated yield and purity of refined product are 80.7% and 100%, respectively, which come to the level of AICl₃ craft at the present time. The estimation of input wastage, output, cost and profit during the craft has been conducted and indicate a good industrial prospect.Last but not least, a one-step method for the preparation of 2-methylanthraquinone and anthraquinone has been explored by employing phthalic anhydride, toluene and benzene as starting materials and HMS zeolite molecule sieve as catalyst in a liquid-solid phase batch reaction condition. It is found that HMS zeolite has good catalytic performance in such a solvent-free reaction condition. The apparent yields of 2-methylanthraquinone and anthraquinone can reach 50% and 41%, respectively, so far. And at the same time, only a little unclosed-ring acylating products are found in the product mixture.更多还原