Syntheses of diphenylmethane derivatives on solid acid catalysts with controlled hydrophobicity, acidity, and reaction space

在疏水性、酸性和反应空间可控的固体酸催化剂上合成二苯甲烷衍生物

基本信息

批准号：
17560683
负责人：
KURIBAYASHI Kiyoshi
金额：
$ 2.29万
依托单位：
Teikyo University of Science & Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

项目摘要

Catalyst heterogenization in syntheses of chemicals by homogeneous catalyses is important from the viewpoint of green chemistry. The purpose of this study is to find suitable solid acid catalysts for the following three reactions in which homogeneous catalysts are used in practical processes:(1) Synthesis of bisphenol F from formaldehyde and phenol, (2) Synthesis of bis(4-hydroxy-3, 5-dimethylphenyl)methane from formaldehyde and 2, 6-dimethylphenol, (3) Synthesis of bis(4-aminophenyl)methane from formaldehyde and aniline. The catalysts examined were various types of zeolite and mesoporous aluminosilicate molecular sieves(Al-MCM-41). All the reactions were carried out in liquid phase at atmospheric pressure. Commercial phenol, 2, 6-dimethylphenol, aniline, and formalin were used as reactants without purification. It is clarified in this study that weak acid sites are responsible for three reactions because of a high reactivity of formaldehyde and the following catalysts and reaction conditions for each reaction are suitable. That is, for reaction (1) the suitable catalysts are high silica H-beta zeolite and Al-MCM-41 and a high phenol/formaldehyde ratio is required to attain a high selectivity, for reaction (2) the suitable catalyst is Al-MCM-41 and the selectivity is almost 100% at any reactant ratios, and for reaction (3) the active catalysts are Al-MCM-41 and H-beta and USY zeolites, the selectivity is affected by reaction spaces, and USY exhibits the highest selectivity.

从绿色化学的角度来看，均相催化合成化学品中的催化剂多相化非常重要。本研究的目的是寻找合适的固体酸催化剂用于以下三个均相催化剂在实际过程中使用的反应：（1）由甲醛和苯酚合成双酚F，（2）双（4-羟基-由甲醛和2, 6-二甲基苯酚合成3, 5-二甲基苯基）甲烷，（3）由甲醛和苯胺合成双（4-氨基苯基）甲烷。所检测的催化剂为各种类型的沸石和介孔铝硅酸盐分子筛(Al-MCM-41)。所有反应均在大气压下在液相中进行。使用市售苯酚、2,6-二甲基苯酚、苯胺和福尔马林作为反应物，无需纯化。这项研究阐明，由于甲醛的高反应活性，弱酸位点负责三个反应，并且每个反应的以下催化剂和反应条件都是合适的。也就是说，对于反应（1），合适的催化剂是高硅H-β沸石和Al-MCM-41，并且需要高苯酚/甲醛比以获得高选择性，对于反应（2），合适的催化剂是Al- MCM-41，在任何反应物比例下选择性几乎为100%，对于反应(3)，活性催化剂为Al-MCM-41和H-beta和USY沸石，选择性受到影响通过反应空间，USY 表现出最高的选择性。