Development of Nanoporous Material-based Heterogeneous Catalysts for Metathesis

纳米孔材料基复分解多相催化剂的开发

• 批准号: 16360399
• 负责人: ONAKA Makoto
• 金额: $ 9.73万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-16360399/
• 关键词: mesoporous alumina; rhenium oxide; methyltrioxorhenium; olefin metathesis; functionalized olefin; acidic support; 不均一系メタセシス触媒; ルイス酸修飾; 塩化亜鉛; 不均一系触媒; 非極性オレフィン; 環境調和型化学合成; Lewis酸性; ナノ空間; 細孔径分布

It was found that mesoporous alumina-supported rhenium oxide (ReO_3/mesoAl_2O_3) had higher catalytic efficiency for the metathesis of simple olefins such as 1-octene and 6-tetradecene without double bond-migration, but that ReO_3/mesoAl_2O_3 was inactive toward olefins having a polar functional group such as ester and ketone.Based on the precedent report that methyltrioxorhenium (MTO) loaded on an acidic support, silica-alumina, showed efficient catalytic activity for the metathesis of olefins with such a polar functional group, in this study mesoporous materials such as mesoporous silica and mesoporous alumina were chemically acidified, and the catalytic activity for the metathesis of functionalized olefins was investigated by using a combination of the acidic mesoporous supports and methyltrioxorhenium. It was revealed that the more acidic the mesoporous support was, the higher catalysis for the metathesis was realized.The mesoporous support can discriminate the molecule sizes of reactant and product olefins since the support has a nanometer-sized homogeneous pores. Therefore, it is expected that the newly developed heterogeneous catalyst system (MTO/acidified mesoporous support) gives us shape-selective metathesis which has not been performed so far.

结果表明，介孔氧化铝负载的氧化铼（ReO_3/mesoAl_2O_3）对1-辛烯和6-十四烯等简单烯烃的合成具有较高的催化效率，且无双键迁移，但对具有极性官能团的酯类和酮类烯烃无催化活性。基于先前报道的负载在酸性载体二氧化硅-氧化铝上的甲基三氧鎓（MTO）对具有这种极性官能团的烯烃的催化活性，本研究对介孔材料如介孔二氧化硅和介孔氧化铝进行化学酸化，并通过酸性介孔载体和甲基三氧鎓的组合来研究功能化烯烃的催化活性。结果表明，介孔载体的酸性越强，催化复分解的效果越好。介孔载体具有纳米尺度的均匀孔隙，可以区分反应物和产物烯烃的分子大小。因此，新开发的多相催化剂体系（MTO/酸化介孔载体）有望实现迄今尚未实现的形状选择性复分解。

项目成果

A new heterogeneous olefin metathesis catalyst composed of rhenium oxide and mesoporous alumina

• DOI: 10.1016/j.micromeso.2004.04.026
• 发表时间: 2004-09
• 期刊: Microporous and Mesoporous Materials
• 影响因子: 5.2
• 作者: T. Oikawa;T. Ookoshi;Tsunehiro Tanaka;Takashi Yamamoto;M. Onaka

固体酸・塩基触媒研究の新しい展開

固体酸碱催化剂研究新进展

• 发表时间: 2005
• 期刊: 有機合成化学協会誌 63
• 作者: 尾中篤;関祐威;増井洋一
• 通讯作者: 増井洋一

Lewis Acid-Modified Mesoporous Alumina : A New Catalyst for Methyltrioxorheniumu in Metathesis of Olefins Bearing Functional Groups

路易斯酸改性介孔氧化铝：带有官能团的烯烃复分解甲基三氧铼的新催化剂

• 发表时间: 2007
• 期刊: J.Organomet.Chem. 692
• 作者: Oikawa;T;Masui;Y;Tanaka;T;Chujo;Y;Onaka,M
• 通讯作者: Onaka,M

Sulfated Mesoporous Alumina : A Highly Effective Solid Strong Base Catalyst for the Tishchenko Reaction in Supercritical Carbon Dioxide

硫酸化介孔氧化铝：一种高效固体强碱催化剂，用于超临界二氧化碳中的 Tishchenko 反应

• 发表时间: 2006
• 期刊: J.Phys.Chem.B 110
• 作者: T.Seki;M.Onaka
• 通讯作者: M.Onaka