芳炔烯基化制烯基芳香化合物用硫酸化的介孔镧锆固体超强酸催化剂的织构和酸性质调控研究

烯基芳香化合物作为重要的精细化学品及中间体在医药、染料、农药、香料、新型高分子材料、天然产品等化学工业领域占据显著地位.芳香化合物与烯基化合物进行反应是该化合物的经典合成方法，但其存在诸多缺陷：(1)芳环需要预活化，如卤代、三氟甲磺酸取代等；(2)产生氢卤酸和无机盐废物，污染环境；(3)原子经济性差.如何高效绿色合成烯基芳香化合物已引起国际学术界的极大兴趣.近年来发现的芳香化合物与炔的烯基化，亦称炔的氢芳化，被认为是颇具应用前景的简单、清洁、原子经济的烯基芳香化合物合成新路线.与烯基芳香化合物的经典合成路线相比，经由芳香化合物与炔的烯基化来合成该目标化合物具有如下优点：(1)芳环无需预活化；(2)不产生氢卤酸和无机盐，合成过程环境友好；(3)原子经济性好(100%).因此，采用芳香化合物与炔的烯基化路线来合成烯基芳香化合物得到了国际学术界的广泛关注.芳香化合物与炔的烯基化反应主要经由两种路径：(1)活化芳环，形成σ-芳基金属络合物；(2)活化炔基，形成烯基阳离子.活化芳环烯基化催化剂的研究主要集中在贵金属盐、贵金属配合物或有机金属.采用贵金属或有机金属催化，活性高、选择性好，但存在价格高、多需昂贵配体、分离和催化剂回收困难、操作条件苛刻等问题，缺乏实用性.酸催化活化炔基是芳香化合物烯基化反应的另一途径.酸催化芳烃烷基化已得以广泛而深入地研究，并在化学工业中占据着突出的历史地位，但酸催化烯基化相关文献报道尚少.相对于酸催化的烷基化，烯基化面临更多挑战.尽管如此，成本低、实用性强的酸催化烯基化路线仍得到了国际学术界的极大关注.但是，仍存在腐蚀设备、污染环境、催化效率差、收率低、催化剂分离困难及炔聚合严重等不足之处.因此，开展清洁、高效、实用的新型烯基化固体酸催化剂的研究意义深远.微孔沸石分子筛克服了液体酸所固有的上述缺点，作为环境友好的固体酸催化剂在烷基化、酰基化等诸多反应中均得到了广泛应用，用于烯基化，存在底物适用范围窄、催化效率低、选择性差和炔聚合严重的问题.以介孔固体酸取代微孔沸石分子筛并结合催化剂微结构和酸性质调控，有望实现对反应底物和烯基化产品的扩散、炔的活化及芳烃与烯基阳离子之间的碰撞过程进行调控，从而解决现有固体酸催化该反应存在的问题.我们开展了芳烃与炔烃的付-克烯基化制烯基芳香化合物用硫酸化的介孔镧锆固体超强酸催化剂的织构和酸性质调控研究.通过介孔镧锆复合氧化物的制备过程参数，如模板剂和氨水的加入量、水热温度、水热时间的调节，来调控硫酸化的介孔镧锆固体超强酸催化剂的织构和酸性质，进而调控固体酸的烯基化催化性能.结果表明，介孔镧锆复合氧化物的制备过程参数对所制备的硫酸化的介孔镧锆固体超强酸催化剂的织构和酸性质影响显著，需要合适的模板剂和氨水的加入量、水热温度、水热时间，才能获得适宜的织构和酸性质.介孔镧锆复合氧化物的最佳制备条件为：模板剂与金属离子摩尔比0.18、氨水与金属离子摩尔比16、水热温度90oC、水热时间60 h.相对于研究组先前报道的硫酸化的介孔镧锆固体超强酸催化剂，经织构和酸性质调控优化的硫酸化的介孔镧锆固体超强酸催化剂的催化活性和稳定性均得以显著提升.采用本文所构筑的固体酸催化剂，用于不同芳香化合物的烯基化，也展示出了良好的催化性能.研究结果表明，具有适宜织构和酸性质的介孔固体酸用于芳香化合物与炔烃的烯基化，来制备烯基芳香化合物，具有很好的发展前景.

Tuning of the textural features and acidic properties of sulfated mesoporous lanthana-zirconia solid acid catalysts for alkenylation of diverse aromatics to their correspondingα-arylstyrenes

The textural features and acidic properties of sulfated mesoporous lanthana‐zirconia solid acids (SO42?/meso‐La0.1Zr0.9Oδ) were efficiently tuned by modifying the conditions used to prepare the meso‐La0.1Zr0.9Oδcomposites, such as the molar ratio of the template to La and Zr metal ions (Nt/m), molar ratio of ammonia to La and Zr metal ions (Na/m), hydrothermal temperature (Thydro), and hy‐drothermal time (thydro). The effect of the textural features and acidic properties on the catalytic performance of solid acid catalysts for alkenylation of p‐xylene with phenylacetylene was investi‐gated. Various characterization techniques such as N2 physisorption, X‐ray diffraction, NH3 temper‐ature‐programmed desorption, and thermogravimetric analysis were employed to reveal the rela‐tionship between the nature of catalyst and its catalytic performance. It was found that the catalytic performance significantly depended on the textural features and acidic properties, which were strongly affected by preparation conditions of the meso‐La0.1Zr0.9Oδcomposite. Appropriate acidic sites and high accessibility were required to obtain satisfactory catalytic reactions for this reaction. It was also found that the average crystallite size of t‐ZrO2 affected by the preparation conditions had significant influence on the ultrastrong acidic sites of the catalysts. The optimized SO42?/meso‐La0.1Zr0.9Oδcatalyst exhibited much superior catalytic activity and coke‐resistant stabil‐ity. Moreover, the developed SO42?/meso‐La0.1Zr0.9Oδcatalyst demonstrated excellent catalytic per‐formance for alkenylation of diverse aromatics with phenylacetylene to their correspondingα‐arylstyrenes. Combining the previously established complete regeneration of used catalysts by a facile calcination process with the improved catalytic properties, the developed SO42?/meso‐La0.1Zr0.9Oδ solid acid could be a potential catalyst for industrial production ofα‐arylstyrenes through clean and atom efficient solid‐acid‐mediated Friedel‐Crafts alkenylation of diverse aromatics with phenylacetylene.