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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.

从绿色化学的观点来看，均相催化合成化学品中的催化剂多相化是一个重要的问题。本研究的目的是寻找合适的固体酸催化剂用于以下三个反应，其中均相催化剂已用于实际生产中：（1）由甲醛和苯酚合成双酚F，（2）由甲醛和2，6-二甲基苯酚合成双（4-羟基-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。所研究的催化剂是各种类型的沸石和中孔铝硅酸盐分子筛（Al-MCM-41）。所有反应均在液相中在大气压下进行。使用商业苯酚、2，6-二甲基苯酚、苯胺和福尔马林作为反应物而无需纯化。在本研究中阐明，弱酸性位点负责三个反应，因为甲醛的高反应性，并且以下催化剂和反应条件适合于每个反应。也就是说，对于反应（1），合适的催化剂是高二氧化硅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，并且在任何反应物比下选择性几乎为100%，并且对于反应（3），活性催化剂是Al-MCM-41和H-β和USY沸石，选择性受反应空间的影响，USY的选择性最高。