Application of supported alkali catalysts in Prins reaction

doi:10.11949/j.issn.0438-1157.20150187

Abstract

Abstract:

Solid base catalysts M_nO/Al₂O₃ (M=Na, K, Cs, Mg, Ca, Sr, n=1 or 2) prepared by impregnation method and C-Cs₂O/Al₂O₃ by co-precipitation method were applied in Prins reaction. Their base amount and pK_a in water were determined. The structure and physico-chemical properties of the carrier and prepared catalysts were characterized by CO₂-TPD, X-ray diffraction, and nitrogen adsorption. The performance of catalysts was evaluated by condensation reaction of isobutene with paraformaldehyde to produce 3-methyl-3-buten-1-ol. The results showed that the performance of catalysts related directly with their basic property and structure. The C-Cs₂O/Al₂O₃ catalyst had stronger basicity and showed superior catalytic performance, and the conversion of formaldehyde and selectivity to MBO reached up to 100.0% and 86.0% respectively. The mechanism of Prins reaction over solid base catalyst was also discussed. The base sites could active the a-H of isobutene, and so could promote the Prins reaction.

Key words: catalyst, solid base, Prins reaction, 3-methyl-3-butene-1-ol, mechanism

摘要：

分别采用浸渍法和共沉淀法制备了负载金属氧化物的固体碱催化剂M_nO/Al₂O₃ (M=Na,K,Cs,Mg,Ca,Sr;n=1,2)和C-Cs₂O/Al₂O₃,测定了催化剂的碱量和pK_a值,分别采用CO₂-TPD、X射线衍射、N₂物理吸附表征了催化剂的物理化学性质。以异丁烯与多聚甲醛经Prins反应制备3-甲基-3-丁烯-1-醇(MBO)为体系考察催化剂活性。结果表明,催化剂的碱性和结构直接影响其催化活性,采用共沉淀法制备的Cs₂O/Al₂O₃催化剂具有更强的碱性,表现出了优越的反应活性,甲醛的转化率和产物MBO的选择性分别为100.0%和86.0%。探讨了固体碱催化反应的机理,发现碱性位可以活化异丁烯的a-H,促进Prins反应。

关键词: 催化剂, 固体碱, Prins反应, 3-甲基-3-丁烯-1-醇, 机理

CLC Number:

TQ426.1

WANG Haiyong, LÜ Hui, LIN Chen, ZHU Zhenwei, XU Kangdong, CAO Guiping. Application of supported alkali catalysts in Prins reaction[J]. CIESC Journal, 2015, 66(10): 3911-3918.

王海永, 吕慧, 林晨, 朱振炜, 许康栋, 曹贵平. 负载碱催化剂在Prins反应中的应用[J]. 化工学报, 2015, 66(10): 3911-3918.

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