双环戊二烯氢甲酰化反应的配体及溶剂效应研究
李娜娜
Subtype硕士
Thesis Advisor高志贤 ; 吾满江·艾力
2014-05-22
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline材料物理与化学
Keyword双环戊二烯 三环癸烷不饱和单醛 三环癸烷二甲醛 配体效应 溶剂效应
Abstract

双环戊二烯(DCPD)主要来源于石油裂解副产C5馏分和煤炭焦化轻苯馏分,通过氢甲酰化反应可以合成一系列的高附加值精细化学品,如三环癸烷不饱和单醛,三环癸烷单甲醇,三环癸烷二甲醛,三环癸烷二甲醇等。本文在烯烃氢甲酰化反应催化剂,膦配体的发展及现状、氢甲酰化反应的溶剂效应总结的基础上,综述了DCPD氢甲酰化反应的研究进展及现实意义。重点探索研究了DCPD氢甲酰化反应中的配体效应和溶剂效应。主要内容和结论如下:
1.根据烯烃氢甲酰化催化剂的研究现状,发展了多相反应均相化的催化剂体系,即铁磁性氧化物担载的钴铑双金属催化剂。
2.以铁磁性氧化物担载的钴铑双金属为催化剂,考察了助催化剂三苯基膦及其衍生物、亚磷酸酯类等膦配体的配体效应,研究表明:吸电子取代基的配体反应速率明显比三苯基膦快,而带有斥电子取代基的配体则会降低反应速率,但是较快的反应速率,对单醛的选择性有所下降;三苯基膦效果较亚磷酸三苯酯好,DCPD转化率为100%,对三环癸烷不饱和单醛的选择性为97.0%。
3. 在三环癸烷二甲醛的合成中,发现两步合成法比一步合成法更有利于DCPD成醛,醛选择性可达99.0%以上。采用两步合成法,以三苯基膦为配体可获得达60.0%的较高二醛选择性,其它两种配体的二醛选择性也优于一步合成法。
4. 对膦配体改性的铁磁性氧化物担载的钴铑双金属催化剂体系进行了考察,探索了不同配体对DCPD氢甲酰化反应的影响。热分析结果显示不同膦配体改性的催化剂形成了不同强度的Rh-P键;结合反应数据发现弱的Rh-P键有利于快速的形成三环癸烷不饱和单醛,而二甲醛的形成则需要一定强度的Rh-P键;这一规律不仅适用于单膦配体、二膦配体,而且适用于不同类型的膦配体。
5. 三环癸烷不饱和单醛的选择性随着反应介质极性的增加呈现下降的趋势,而三环癸烷二甲醛的选择性随着反应介质极性的增加呈现先增加后降低的趋势,在极性为5.4的丙酮反应介质中达到极大值;反应介质的极性对三环癸烷单醛的生成速率的影响比三环癸烷二甲醛大得多。

Other Abstract

Dicyclopentadiene (DCPD) mostly comes from both the C5 fraction by-product of ethylenecracking process and light benzene fraction of the coal-coking process. A series of value-added fine chemicals such astricyclodecanedimethylol, tricyclodecanedicarboxylic acid and their polyesterderivatives could be synthesized using DCPD as the starting materialby means of the hydroformylation, followed by hydrogenation. In this thesis, the practical significance and the recent developments of the olefin hydroformylation and its catalysts, the developments of phosphine ligands, the solvent effect were reviewed. The effect of the ligands and solvents on the DCPD hydroformylation were systematically investigated. The mechanism was proposed and discussed. The main results and conclusions are as follows: 1. The magnetic iron oxide supported cobalt and rhodium bimetal catalyst were developed based on the principle of the homogenizing heterogeneous reaction. 2. The ligand effects were investigated with Co-Rh/Fe3O4 as the catalyst, phosphites, triphenylphosphine(PPh3) and its dirivatives were used as the ligands. The results showed that the ligands with electron withdrawing substituents have a significant higher reaction rate, while ligands with electron donating substituents lead to lower reaction rate; but poor selectivity were detected when the reaction was performed at a higher reaction rate. 100% DCPD conversion and 97.0% unsaturated monoformyltricyclodecanes(MFTD) selectivity were achieved with PPh3 as the ligand, which was the best results among the ligands that used in this work. 3. Synthesis of diformyltricyclodecane (DFTD) was carried out by means of one-step method and two-step method. The results indicated that a 99.0% selectivity of total aldehyde could be obtained through the two-step method, which was superior to one step method. 60% DFTD selectivity could be reached with PPh3 as the ligand, which was the best candidate among all the ligands. 4. The effects of different ligands on DCPD hydroformylation reaction were investigated over the cobalt and rhodium bimetallic catalyst modified with various ligands. The results of thermal analysis showed that different decomposition temperature was observed on the catalysts modified with various phosphine ligands. The decomposition temperature denoted the corresponding Rh-P bond strength, and it correlated well with its catalytic performance. Thus, it has been proposed that a weak Rh-P bond was favored to form MFTD with a fast reaction rate, while a relatively stronger Rh-P bond was highly required for the synthesis of DFTD. Besides the PPh3 series, other ligands demonstrated the same rule that a weak Rh-P bond led to a fast reaction rate for MFTD synthesis 5. The effects of solvents on the synthesis of MFTD and DFTD by hydroformylation of DCPD were investigated on the Co-Rh/Fe3O4 catalyst modified with PPh3. The results showed that the polarity of solvent has a significant influence on the reaction rate and the target product selectivity. The reaction rate of MFTD increased with increasing polarity of the solvents. However, the formation rate and selectivity of DFTD increased at first, then decreased with a higher polarity solvent; and a higher DFTD selectivity could be obtained with acetone of 5.4 polarity as the solvent. In additional, a siganificant influence for MFTD synthesis was observed with various polar solvents.

Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/3414
Collection新疆维吾尔自治区精细化工工程技术研究中心
Affiliation中国科学院新疆理化技术研究所
Recommended Citation
GB/T 7714
李娜娜. 双环戊二烯氢甲酰化反应的配体及溶剂效应研究[D]. 北京. 中国科学院大学,2014.
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