本文選題：介孔固體酸 + 烯基化��； 參考：《催化學(xué)報(bào)》2016年08期

【摘要】：烯基芳香化合物作為重要的精細(xì)化學(xué)品及中間體在醫(yī)藥、染料、農(nóng)藥、香料、新型高分子材料、天然產(chǎn)品等化學(xué)工業(yè)領(lǐng)域占據(jù)顯著地位.芳香化合物與烯基化合物進(jìn)行反應(yīng)是該化合物的經(jīng)典合成方法,但其存在諸多缺陷:(1)芳環(huán)需要預(yù)活化,如鹵代、三氟甲磺酸取代等;(2)產(chǎn)生氫鹵酸和無機(jī)鹽廢物,污染環(huán)境;(3)原子經(jīng)濟(jì)性差.如何高效綠色合成烯基芳香化合物已引起國際學(xué)術(shù)界的極大興趣.近年來發(fā)現(xiàn)的芳香化合物與炔的烯基化,亦稱炔的氫芳化,被認(rèn)為是頗具應(yīng)用前景的簡單、清潔、原子經(jīng)濟(jì)的烯基芳香化合物合成新路線.與烯基芳香化合物的經(jīng)典合成路線相比,經(jīng)由芳香化合物與炔的烯基化來合成該目標(biāo)化合物具有如下優(yōu)點(diǎn):(1)芳環(huán)無需預(yù)活化;(2)不產(chǎn)生氫鹵酸和無機(jī)鹽,合成過程環(huán)境友好;(3)原子經(jīng)濟(jì)性好(100%).因此,采用芳香化合物與炔的烯基化路線來合成烯基芳香化合物得到了國際學(xué)術(shù)界的廣泛關(guān)注.芳香化合物與炔的烯基化反應(yīng)主要經(jīng)由兩種路徑:(1)活化芳環(huán),形成σ-芳基金屬絡(luò)合物;(2)活化炔基,形成烯基陽離子.活化芳環(huán)烯基化催化劑的研究主要集中在貴金屬鹽、貴金屬配合物或有機(jī)金屬.采用貴金屬或有機(jī)金屬催化,活性高、選擇性好,但存在價(jià)格高、多需昂貴配體、分離和催化劑回收困難、操作條件苛刻等問題,缺乏實(shí)用性.酸催化活化炔基是芳香化合物烯基化反應(yīng)的另一途徑.酸催化芳烴烷基化已得以廣泛而深入地研究,并在化學(xué)工業(yè)中占據(jù)著突出的歷史地位,但酸催化烯基化相關(guān)文獻(xiàn)報(bào)道尚少.相對于酸催化的烷基化,烯基化面臨更多挑戰(zhàn).盡管如此,成本低、實(shí)用性強(qiáng)的酸催化烯基化路線仍得到了國際學(xué)術(shù)界的極大關(guān)注.但是,仍存在腐蝕設(shè)備、污染環(huán)境、催化效率差、收率低、催化劑分離困難及炔聚合嚴(yán)重等不足之處.因此,開展清潔、高效、實(shí)用的新型烯基化固體酸催化劑的研究意義深遠(yuǎn).微孔沸石分子篩克服了液體酸所固有的上述缺點(diǎn),作為環(huán)境友好的固體酸催化劑在烷基化、酰基化等諸多反應(yīng)中均得到了廣泛應(yīng)用,用于烯基化,存在底物適用范圍窄、催化效率低、選擇性差和炔聚合嚴(yán)重的問題.以介孔固體酸取代微孔沸石分子篩并結(jié)合催化劑微結(jié)構(gòu)和酸性質(zhì)調(diào)控,有望實(shí)現(xiàn)對反應(yīng)底物和烯基化產(chǎn)品的擴(kuò)散、炔的活化及芳烴與烯基陽離子之間的碰撞過程進(jìn)行調(diào)控,從而解決現(xiàn)有固體酸催化該反應(yīng)存在的問題.我們開展了芳烴與炔烴的付-克烯基化制烯基芳香化合物用硫酸化的介孔鑭鋯固體超強(qiáng)酸催化劑的織構(gòu)和酸性質(zhì)調(diào)控研究.通過介孔鑭鋯復(fù)合氧化物的制備過程參數(shù),如模板劑和氨水的加入量、水熱溫度、水熱時(shí)間的調(diào)節(jié),來調(diào)控硫酸化的介孔鑭鋯固體超強(qiáng)酸催化劑的織構(gòu)和酸性質(zhì),進(jìn)而調(diào)控固體酸的烯基化催化性能.結(jié)果表明,介孔鑭鋯復(fù)合氧化物的制備過程參數(shù)對所制備的硫酸化的介孔鑭鋯固體超強(qiáng)酸催化劑的織構(gòu)和酸性質(zhì)影響顯著,需要合適的模板劑和氨水的加入量、水熱溫度、水熱時(shí)間,才能獲得適宜的織構(gòu)和酸性質(zhì).介孔鑭鋯復(fù)合氧化物的最佳制備條件為:模板劑與金屬離子摩爾比0.18、氨水與金屬離子摩爾比16、水熱溫度90oC、水熱時(shí)間60h.相對于研究組先前報(bào)道的硫酸化的介孔鑭鋯固體超強(qiáng)酸催化劑,經(jīng)織構(gòu)和酸性質(zhì)調(diào)控優(yōu)化的硫酸化的介孔鑭鋯固體超強(qiáng)酸催化劑的催化活性和穩(wěn)定性均得以顯著提升.采用本文所構(gòu)筑的固體酸催化劑,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.研究結(jié)果表明,具有適宜織構(gòu)和酸性質(zhì)的介孔固體酸用于芳香化合物與炔烴的烯基化,來制備烯基芳香化合物,具有很好的發(fā)展前景.
[Abstract]:As an important fine chemical and intermediate, alkenyl aromatic compounds occupy a significant position in the fields of medicine, dyes, pesticides, spices, new polymer materials, natural products and other chemical industries. The reaction of aromatic compounds with alkenyl compounds is the classic synthesis method of the compound, but there are many defects in it: (1) the aromatics need to be pre activated. Such as halogenation, substitution of three fluorine mesylate and so on; (2) producing halogenic acid and inorganic salt waste, polluting the environment; (3) poor atomic economy. How efficient green synthesis of alkenyl aromatic compounds has aroused great interest in the international academic circle. In recent years, the aromatization of aromatic compounds and alkynes, also known as alkynes, is considered to be a promising application. A new route for the synthesis of alkenyl aromatic compounds in simple, clean, atomic economy. Compared with the classical synthetic route of alkenyl aromatic compounds, the synthesis of the target compound via aromatic compounds and alkynes has the following advantages: (1) no aromatics need to be preactivated; (2) no hydrogen halide and inorganic salts are produced, and the synthesis process is environmentally friendly; (3) atoms Good economic (100%). Therefore, the enyl aromatic compounds with aromatic compounds and alkynes have been widely concerned in the international academic circle. The alkylation of aromatic compounds and alkynes is mainly via two ways: (1) activating aromatic rings to form a sigma aryl foundation complex; (2) activating alkynyl, forming alkyl cation. Activation aromatics. The studies of cycloalkylation catalysts are mainly concentrated in precious metal salts, noble metal complexes or organic metals. They are catalyzed by precious metals or organometallic metals, are highly active and selective, but have high prices, more expensive ligands, difficult separation and catalyst recovery, harsh operating conditions, and lack of practicability. Acid catalyzed activation of alkynes is aromatic. Acid catalyzed alkylation of aromatic hydrocarbons has been widely and deeply studied and occupies a prominent historical position in the chemical industry, but there are few reports on alkylation related to acid catalyzed alkylation. Alkylation is faced with more challenges than acid catalyzed alkylation. Nevertheless, low cost and practical acid catalysis However, there are still some deficiencies in corrosion equipment, environmental pollution, poor catalytic efficiency, low yield, difficult separation of catalyst and serious alkyne polymerization. Therefore, the development of a clean, efficient and practical novel alkylated solid acid catalyst is of profound significance. As a environmentally friendly solid acid catalyst, it has been widely used in alkylation and acylation as a environmentally friendly catalyst. It is used in alkylation, with narrow application scope, low catalytic efficiency, poor selectivity and severe polymerization of alkynes. The microstructures and acid properties of the chemicals are regulated, and it is expected to realize the diffusion of reaction substrates and alkylated products, the activation of alkynes and the collision process between aryl and alkenyl cations, so as to solve the existing problems of the existing solid acid catalyzing the reaction. The study on the texture and acid properties of acidified mesoporous lanthanum zirconium solid superacid catalysts. Through the preparation process parameters of mesoporous lanthanum zirconium composite oxides, such as the addition of template and ammonia, hydrothermal temperature, and hydrothermal time regulation, the texture and acid properties of the sulfated mesoporous lanthanum zirconium solid superacid catalysts are regulated and regulated. The results show that the preparation process parameters of mesoporous lanthanum zirconium composite oxides have significant influence on the texture and acid properties of the sulfated mesoporous lanthanum zirconium solid superacid catalyst. The suitable formwork and ammonia water content, the hydrothermal temperature and the hydrothermal time can be used to obtain the suitable texture and acidity. The optimum preparation conditions for the mesoporous lanthanum zirconium composite oxide are: the molar ratio of template to metal ion 0.18, the molar ratio of ammonia to metal ions 16, the hydrothermal temperature 90oC and the hydrothermal time 60h. relative to the sulfated mesoporous lanthanum zirconium solid superacid catalyst previously reported by the research group, and the sulfated mesoporous lanthanum, which are optimized by the texture and acid properties. The catalytic activity and stability of the zirconium solid superacid catalyst have been greatly improved. The solid acid catalyst constructed in this paper has been used for the alkylation of different aromatic compounds and shows good catalytic performance. The results show that the mesoporous solid acids, which are suitable for texture and acid properties, are used in aromatic and alkyne alkenes. The preparation of alkenyl aromatic compounds is of great potential for development.
【作者單位】： 大連理工大學(xué)化工與環(huán)境生命學(xué)部精細(xì)化工國家重點(diǎn)實(shí)驗(yàn)室;
【基金】：financially supported by the National Natural Science Foundation of China (21276041) the Program for New Century Excellent Talents in University of Ministry of Education (NCET-12-0079) the Natural Science Foundation of Liaoning Province (2015020200) the Fundamental Research Funds for the Central Universities (DUT15LK41)~~
【分類號】：O643.36

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