Preparation of Organo-Functionalized Mesoporous Zeolites Supported Phosphine-Rhodium Complex and Their Catalytic Performance for Hexene-1 Hydroformylation

制备了表面有机官能团化的MCM 4 1和MCM 4 8介孔分子筛以及SiO2 等载体固载铑膦配合物催化剂 ,考察了所制备催化剂对液相己烯 1氢甲酰化的催化性能 ,并用X射线衍射、BET、红外光谱和原子吸收光谱等技术对载体和催化剂的组成和结构进行了表征 .结果表明 ,固载化铑膦配合物对烯烃氢甲酰化的催化性能与有机官能团的种类及载体的结构有关 ;固载于含胺基和腈基有机官能团化介孔分子筛载体的铑膦配合物表现出较高的催化活性和稳定性 .Organo-functionalized mesoporous zeolites MCM-41 and MCM-48, and amorphous SiO 2 were used as supports to prepare heterogenized phosphine-rhodium complex via anchoring for the hydrofomylation of hexene-1. The supports and the catalysts were characterized by means of XRD, BET, FT-IR and AAS. The MCM-41 and MCM-48 were functionalized with silanes containing (mono-, di-, tri-) amino-, mercapto- and nitrile- groups, respectively, without destruction of the mesoporous structure of the zeolites. The catalytic performance of the catalysts was related to the structure of organo-groups and also to the structural features of the supports. Higher catalytic activity and selectivity for n-C 6H 13CHO were obtained in the case of the catalysts using the mesoporous zeolites functionalized with amino- and nitrile-silanes as supports. No significant decrease in the catalytic performance of the phosphine-rhodium complex immobilized on the amino-functionalized mesoporous zeolites used repeatedly for 6 times was observed.国家自然科学基金 (2 0 0 2 3 0 0 1,2 0 0 2 10 0 2 );; 国家重点基础研究发展规划 (G2 0 0 0 0 480 0 8)资助项

HYDROFORMYLATION OF 1-HEXENE BY NOVEL IMINOPHOSPHINE RHODIUM COMPLEXES

通讯联系人: 袁友珠, Tel:05922184565;E-mail: [email protected][中文文摘]采用还原胺化法合成了新型膦氮配体铑配合物,并采用FT-IR和NMR(1H,13C,31P)进行结构表征。考察了水含量对膦氮配体铑配合物催化1-己烯氢甲酰化反应的影响,以及各种酸处理对催化剂循环使用的效果。结果表明,适量的水可提高膦氮配体铑配合物对1-己烯氢甲酰化反应的催化活性和选择性。反应后的膦氮配体铑配合物催化剂用适当有机酸萃取进入水相与产物分离,然后改变pH值使其从水相再进入新鲜有机溶剂中,实现催化剂在催化高碳烯烃氢甲酰化反应中的循环使用。[英文文摘]Novel iminophosphine ligands(P-N ligands) were synthesized and characterized by IR and NMR(1H,13C,31P).The effect of water content on 1-hexene hydroformylation catalyzed by P-N ligand-Rh complexes was investigated,at the same time,the recycling of the catalysts based on these iminophosphines was examined.The results revealed that the addition of certain amount of water into 1-hexene hydroformylation system,the catalytic activity and selectivity of P-N ligand-Rh complexes could be enhanced.After 1-hexene hydroformylation,the catalyst was extracted by organic acid into water and back by setting the pH of the aqueous phase to the po int at w hich the complex was no longer water-soluble to realize its recycling. extracted into fresh organic solvent国家自然科学基金项目(20021002和20873108)资

HYDROFORMYLATION OF 1-HEXENE BY NOVEL IMINOPHOSPHINE

袁友珠, Tel : 0592-2184565; Email: yzyuan@ xmu. edu. cn[中文摘要]采用还原胺化法合成了新型膦氮配体铑配合物, 并采用FT-IR 和NMR (1H,13C,31P)进行结构表征。考察了水含量对膦氮配体铑配合物催化1-己烯氢甲酰化反应的影响, 以及各种酸处理对催化剂循环使用的效果。结果表明, 适量的水可提高膦氮配体铑配合物对1-己烯氢甲酰化反应的催化活性和选择性。反应后的膦氮配体铑配合物催化剂用适当有机酸萃取进入水相与产物分离, 然后改变pH 值使其从水相再进入新鲜有机溶剂中, 实现催化剂在催化高碳烯烃氢甲酰化反应中的循环使用。 [英文摘要]Novel iminophosphine ligands (P-N ligands) were synthesized and characterized by IR and NMR(1H,13C,31 P).The effect of water content on 1-hexene hydroformylation catalyzed by P-N ligand-Rh complexes was investigated, at the same time,the recycling of the catalysts based on these iminophosphines was examined. The results revealed that the addition of certain amount of water into 1-hexene hydroformylat ion sy stem, the catalyt ic act ivity and selectivity of P-N ligand-Rh complexes could be enhanced. After 1-hexene hy dro formylat ion, the catalyst was extracted by organic acid into water and back extracted into fresh organic solvent by setting the pH of the aqueous phase to the point at which the complex was no longer watersoluble to realize its recycling .国家自然科学基金项目( 20021002 和20873108) 资

Catalytic Properties of Ultrafine SiO_2 Supported Amphiphilic Phosphine-Rh Complex Catalysts

作者简介: 彭庆蓉( 1973- ) , 女, 四川达州市, 讲师, 博士。 通讯联系人：袁友珠[中文文摘]针对均相催化反应后催化剂与产物分离困难和高碳烯烃在水-有机两相中反应速率较低的问题,采用水-有机两亲膦铑络合物负载到超细SiO2载体上催化1-己烯氢甲酰化反应,并与超细SiO2制备负载水相催化剂比较,超细SiO2负载型两亲铑膦络合物催化剂表现出较高的1-己烯氢甲酰化反应活性和选择性,且含水质量分数范围较宽,反应后产物与催化剂容易分离。两亲膦铑络合物超细SiO2负载液相催化剂可避免超细SiO2负载水相催化剂循环使用时水分被提取到有机相的缺点,同时获得较高的氢甲酰化反应活性和选择性。[英文文摘]Because of the lower activity of higher olefins in aqueous/organic biphasic catalysis system and the catalyst separation of homogeneous catalysts,ultrafine SiO2 nanoparticles were used as supports to immobilize amphiphilic phosphine-complex to obtain supported catalysts for hydroformylation of 1-hexene. Compared to the supported aqueous-phase catalysts (SAPC) on ultrafine SiO2 support,the ultrafine SiO2-supported catalyst with amphiphilic phosphine-complex presented a higher hydroformylation performance over a relatively wider range of support hydration. Since the water was distilled to organic phase for more times recycled catalysts, the draw backs of ultrafine SiO2 supported water- soluble phosphine-Rh complexes catalyst could be avoided by using supported liquid- phase catalyst prepared by using amphiphilic phosphine- Rh complexes, obtaining higher activity and selectivity of hydroformylation.国家自然科学基金(20023001

Study on Ultrafine SiO_2 Supported Water-soluble Phosphine-Rh Complex Catalysts

用超细 Si O2 负载水溶性铑膦配合物 ,并研究其对 1-己烯氢甲酰化的催化性能 .实验结果表明 ,粒径为10～ 2 0 nm的超细 Si O2 负载水溶性铑膦配合物所表现的催化活性比颗粒 Si O2 负载型催化剂高 3倍多 ,且可在较宽的含水量范围内保持高反应活性 .当膦铑摩尔比为 5 0 ,超细 Si O2 负载型催化剂含水量为 2 5 %～ 5 5 % (质量分数 )、烯铑摩尔比为 2 5 0 0、反应温度 373K和 CO/H2 (1/1,体积比 )压力 4.0 MPa的反应条件下 ,其 1-己烯氢甲酰化的反应转化数为 45 0 h- 1 ,产物醛的选择性为 10 0 % ,醛的 n/i比值达 3.2In this work an ultrafine SiO\-2 supported water\|soluble phosphine\|Rh complexes catalyst (ultrafine\|SiO\-2\|SAPC) has been developed for hydroformylation of 1\|hexene. The experimental results show that the ultrafine\|SiO\-2\|SAPC catalyst prepared by using SiO\-2 powder with particle sizes of 10~20 nm exhibits remarkably higher activity as compared to the reported granular SiO\-2\|SAPC catalyst and can maintain high activity with in wider range of water contents. An average TOF of a 450 h -1 run of 1\|hexene hydroformylation, where the selectivity to aldehyde is 100% and aldehyde n/i ratio is about 3.2, is obtained on the ultrafine\|SiO\-2\|SAPC containing 25%~55% of water under P/Rh(molar ratio)=50, 1\|hexene/\{Rh(molar ratio)=\}2 500, reaction temperature 373 K, and CO/H\-2 (1/1, volume ratio) pressure 4.0 MPa.国家重点基础发展规划项目 ( G2 0 0 0 0 480 0 8);; 国家创新研究群体科学基金 ( 2 0 0 2 10 0 2 ) ;; 教育部优秀年轻教师基金及骨干教师基金资助课

Hydroformylation of 1-Hexene with Water-soluble Phosphine- rhodium Complexes in Room Temperature Ionic Liquids

研究了水溶性膦配体铑配合物在若干离子液体中的1 己烯氢甲酰化反应性能.通过改变离子液体的阴阳离子结构,可使水溶性TPPTS 铑配合物在离子液体中表现出较高的1 己烯氢甲酰化反应活性和选择性;在[BMI]BF4离子液体中加入适量的水,可提高TPPTS 铑配合物的催化活性;在[BMI]BF4离子液体中,水/有机两亲性膦配体与铑形成的配合物,反应后催化剂与产物自动分层,实现催化剂的循环使用.本文结果表明,水溶性膦配体铑配合物的催化活性与其在离子液体中的溶解度密切相关.This paper studied the catalytic performances of water-soluble phosphine-rhodium complexes in room temperature ionic liquids for 1-hexene hydroformylation. The higher reaction rate and normal aldehyde selectivity were obtained through choosing the proper anionic and cationic groups of the ionic liquids. Moreover, the catalytic activity of TPPTS-rhodium complex could be increased by increasing the solubility of TPPTS in the ionic liquids like [BMI]BF_4 and also by the addition of small amount of water into the [BMI]BF_4 ionic liquid. The recycling of the catalysts based amphiphilic phosphines was achieved in the [BMI]BF_4 ionic liquid without significant loss in the catalytic activity due to the easy phase separation. The experimental results inferred that the solubility of water-soluble rhodium complexes was key to obtain the reasonable catalytic activity.国家重点基础发展规划(G2000048008);; 国家自然科学基金(20021002)资助项目