【作者】 杨勇；

【导师】 袁友珠；

【作者基本信息】 厦门大学 ， 物理化学， 2006， 博士

【摘要】 本学位论文选择长链烯烃氢甲酰化制高碳醛为目标反应,以介孔分子筛MCM-41、MCM-48和SBA-15及SiO₂等为载体,通过表面键联有机官能团和离子液体,固载化油溶性铑膦配合物;在此基础上,制备了担载离子液体?水溶性铑膦配合物催化剂（即担载型离子液体液膜催化剂,记为SILPCs）。结合XRD、BET、FTIR、AAS、XPS、SEM、HRTEM、TGA-DSC、NMR等表征的结果,关联研究催化剂结构与反应活性、选择性和稳定性,为研制长链烯烃氢甲酰化新型多相化催化剂提供科学基础。1、在介孔分子筛等表面用若干不同结构单元的有机官能团进行修饰,如,-（CH₂）₃SH、-（CH₂）₃CN、-（CH₂）₃NH₂、-（CH₂）₂NH（CH₂）₃NH₂等,继而通过与HRh（CO）（PPh₃）₃的相互作用,获得固载化铑膦配合物催化剂。结果表明,介孔分子筛经有机官能团修饰并固载铑膦配合物后,保持分子筛特有的骨架和规整孔道结构,可提供反应分子扩散与反应的适度空间,产生足够高的反应活性;催化性能与有机官能团种类及载体的结构有关,铑膦配合物固载于含双胺基和腈基有机官能团化介孔分子筛载体表面,表现出较好的催化活性;并且,表面有机官能团（尤其是孔道内的胺基官能团）与铑膦物种之间存在的较强相互作用,使铑配合物获得了较牢靠的固载化;和均相Wilkinson催化剂相比,固载化铑膦配合物的烯烃氢甲酰化催化活性虽有较大幅度的降低,但这种多相化催化剂与产物分离简单,可循环使用,多次循环复用的总反应转化数高于相应的均相催化剂。2、在介孔分子筛等表面化学键联离子液体,使离子液体多相化,进而将铑膦配合物HRh（CO）（PPh₃）₃固载于表面离子液体层中,制得载体表面键联离子液体负载型催化剂。结果表明,这种多相化途径,亦可使铑膦配合物物种在反应过程中不易脱落,其催化活性和选择性略高于前述的有机官能化载体负载型催化剂,且在一定程度上实现了催化剂的简单分离和循环使用;与此对比,采用未键联离子液体的载体所制备的负载型催化剂,在循环复用过程则快速失活。3、利用离子液体和水溶性铑膦配合物的特点,将水溶性单、双齿膦配体及其铑配合物溶解于离子液体中,进而直接担载到MCM-41等载体表面,制得SILPCs。结果表明,介孔分子筛载体的规整结构在合适的离子液体中及负载前后无明显改变,而其大的比表面和规整孔道有利于反应活性和选择性的提高;催化活性与离子液体的负载量、铑膦摩尔比、载体的结构及其膦配体结构关系较大,而与离子液体种类的关系较小;采用合适结构的水溶性双齿膦如sulfoxantphos为配体,所制得催化剂表现出很高的正构醛选择性,例如,在同等条件下,1-己烯烃氢甲酰化生成的庚醛n/i是采用水溶性单齿膦TPPTS为配体所得催化剂的7倍多。进一步的实验结果证实,存在于载体表面离子液体中的水溶性铑膦配合物结构稳定,在多次催化循环使用中,催化活性和选择性无明显下降趋势。更多还原

【Abstract】 This dissertation has set the hydroformylation of higher olefins as the object of study. The organic-soluble phosphine-rhodium complex has been supported on the organo- and ionic liquid （IL）-grafted onto the surfaces of mesoporous silicas such as MCM-41, MCM-48 and SBA-15 and conventional SiO₂. Thereafter, supported IL phase catalysts （SILPCs） have been prepared by direct co-immobilization of water-soluble phosphine-rhodium complex and IL onto the mesoporous silicas and SiO₂. The supports and the catalysts were characterized by means of XRD, BET, FTIR, AAS, XPS, SEM, HRTEM, TAG-DSC and NMR to correlate the catalytic performance and the structure of catalysts. The aim of the studies was to explore the possibility of developing novel heterogenized catalysts for the hydroformylation of higher olefins.1. Organo-functionalized mesoporous silicas with silanes containing （mono-, di-）amino, mercapto and nitrile groups, respectively, were used as supports to prepare heterogeneized Wilkinson phosphine-rhodium complex catalysts. Evidences from the experiments revealed that the mesoporous silicas retained their skeleton and ordered mesoporous structures after the organo-functionalization and Rh-P complex encapsulation. The remained channels were enough for the diffusion and reaction of substrates. The catalytic performance was influenced by the structure of organic groups and those containing di-amino and nitrile groups as supports showed better catalytic activity. A strong interaction occurred between the amino-groups, particularly those at the internal walls of mesoporous silicas, and P-Rh complex, resulting in forming the stable heterogenized catalysts. Such catalysts afforded relatively lower TOF than that of the corresponding homogeneous complex, but they could be easily separated from the reactants and reused many times without significant deactivation. The accumulative TON was higher than that of homogeneous counterpart.2. The mesoporous silicas grafted with IL were used as supports for immobilization of Rh-P complex. The results showed that the Rh-P complex could stay stably in the IL layer at the surfaces, forming an alternative kind of heterogenized catalysts that were active for the hydroformylation of higher olefins and showed no significant leaching of active species in the process of reaction. Moreover, they exhibited better catalytic activity than that of above heterogenized catalysts and also could be reused several times without considerable reduction in the catalytic performance. In contrast, the drastic deactivation was observed during the catalyst recycling with the non-grafted mesoporous silicas as supports.更多还原