羟基磷灰石负载HRh(CO)(TPPTS)_3催化1-己烯氢甲酰化反应——高选择性和特殊的异构化功能

HRhCO(TPPTS)_3/HAP Hydroformylate 1-Hexene——High Selectivity and Special Isomerization Performance

采用浸渍法制备了以羟基磷灰石(HAP)载型水溶性铑络合物HRh(CO)(TPPTS)3/HAP催化剂(TPPTS=三苯基膦三间磺酸钠),采用傅里叶变换红外光谱(FTIR)、固体核磁共振波谱(31P CP-MASNMR)、扫描电子显微镜(SEM)、电感耦合等离子发射光谱(ICP-OES)和比表面积测定(BET)等对催化剂进行了表征.该催化剂在催化1-己烯氢甲酰化反应中表现出高活性和高选择性,在优化条件下获得了100%的醛选择性和高转化频率(TOF=2465 h-1).该催化剂还对1-己烯、2-己烯和3-己烯表现出特殊的异构化功能.该催化剂制备方法简单,通过简单离心分离可以循环使用.对HAP负载HRh(CO)(TPPTS)3的原理以及催化剂对烯烃异构化的机理进行了探讨.

Water-soluble rhodium-phoshpine complex HRhCO （TPPTS）3 and TPPTS were supported by hydroxyapatite（HAP）. The catalysts were characterized by FTIR, solid state 31p CP-MAS NMR, SEM, ICP- OES, and N2 adsorption-desorption measurements. The catalysts showed special isomerization performance for 1-hexene, 2-hexene and 3-hexene. The results show high activity and selectivity in the hydroformylation of 1-hexene. Selectivity of 100% of aldehydes and high turnover frequency（TOF=2465 h-1 ） were obtained under optimum condition. The catalysts could be easily separated from organic products and reused. The mechanism of isomerization performance of the catalyst and supporting HRhCO （TPPTS）3 on HAP were discussed.