Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quater...Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quaternary ammoniums bearing different cationic sizes,i.e.MTOA+(methyltrioctylammonium,[(C_(8)H_(17))_(3)CH_(3)N]+),HTMA+(hexadecyltrimethylammonium,[(C_(16)H_(33))(CH_(3))_(3)N]+) and DMDOA+(dimethyldioctadecylammonium,[(C_(18)H_(37))_(2)(CH_(3))_(2)N]+) were incorporated with polyoxometalate (POM) anions to prepare phase transfer catalysts (PTCs),which were used in the styrene epoxidations.Among them,(MTOA)_(3)PW_(4)O_(24)exhibits the best catalytic performance judged from the highest styrene conversion rate(52%) and styrene oxide selectivity (93%),during which the styrene epoxidation conditions were optimized.Meanwhile,the deactivation mechanism of this kind of PTCs was proposed firstly,i.e.in the case of low H_(2)O_(2) content,the oxidant can only be used in the styrene epoxidation,in which the catalyst can transform into stable Keggin-type POM.But when the content of H_(2)O_(2) is higher,the excess H_(2)O_(2) can reactivate the Keggin-type POM into active (PW_(4)O_(24))_(3)-anions,which can trigger the ring-opening polymerization of styrene oxide.Consequently,the catalyst is deactivated by adhered poly(styrene oxide)irreversibly,which was determined by NMR spectra.In this situation,the active moiety{PO_(4)[WO(O_(2))_(2)]_(4)}_(3)-in phase-transfer catalytic system can break into some unidentified species with low W/P ratio with the presence of epoxides.This work will be beneficial for the design of new PTCs in alkene epoxidation in fine chemical industry.展开更多
The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variat...The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variations in the catalyst structure and morphology with pH values were characterized by X-ray power diffraction,nitrogen adsorption-desorption analysis,transmission electron microscopy and X-ray photoelectron spectroscopy.As the pH value applied during the initial synthesis,the resulting Cu-KIT-6_x exhibited different structural,textural and surface characteristics,especially in terms of specific copper species and copper content At a pH value of 3.78,approximately 4.6 wt%copper（Ⅱ） was successfully incorporated into the framework of the initial KIT-6,in the form of-Cu-O-Si- groups.The catalytic performance of each catalyst was evaluated by following the epoxidation of styrene,employing tert-butyl hydroperoxide as the oxidant and CH_3CN as the solvent.A significant styrene conversion of 43.5%with 86.6%selectivity for the desired styrene epoxide was obtained over the Cu-KIT-63.78.A higher Cu content,an ordered cubic laid mesoporous architecture and various specific textural characteristics all combined to endow the Cu-KIT-63.78 with high catalytic activity and good stability.展开更多
The polymerization of styrene is monitored by pyrene excimer formation. The ratio of monomer to excimer intensities ( I m/ I e) of pyrene increases as polymerization proceeds. The increase of I m/ I e...The polymerization of styrene is monitored by pyrene excimer formation. The ratio of monomer to excimer intensities ( I m/ I e) of pyrene increases as polymerization proceeds. The increase of I m/ I e is ascribed to the increase of microviscosity surrounding the probes forming excimer during polymerization. The linear relationship between the changing rate of I m/ I e and the polymerization rate of styrene is obtained. Therefore, I m/ I e may be used to monitor the progress of the polymerization of styrene.展开更多
基金financial supported by the National Natural Science Foundation of China (22078065)Key Program of Qingyuan Innovation Laboratory (00221001)Quanzhou City Science & Technology Program of China (2020C008R)。
文摘Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quaternary ammoniums bearing different cationic sizes,i.e.MTOA+(methyltrioctylammonium,[(C_(8)H_(17))_(3)CH_(3)N]+),HTMA+(hexadecyltrimethylammonium,[(C_(16)H_(33))(CH_(3))_(3)N]+) and DMDOA+(dimethyldioctadecylammonium,[(C_(18)H_(37))_(2)(CH_(3))_(2)N]+) were incorporated with polyoxometalate (POM) anions to prepare phase transfer catalysts (PTCs),which were used in the styrene epoxidations.Among them,(MTOA)_(3)PW_(4)O_(24)exhibits the best catalytic performance judged from the highest styrene conversion rate(52%) and styrene oxide selectivity (93%),during which the styrene epoxidation conditions were optimized.Meanwhile,the deactivation mechanism of this kind of PTCs was proposed firstly,i.e.in the case of low H_(2)O_(2) content,the oxidant can only be used in the styrene epoxidation,in which the catalyst can transform into stable Keggin-type POM.But when the content of H_(2)O_(2) is higher,the excess H_(2)O_(2) can reactivate the Keggin-type POM into active (PW_(4)O_(24))_(3)-anions,which can trigger the ring-opening polymerization of styrene oxide.Consequently,the catalyst is deactivated by adhered poly(styrene oxide)irreversibly,which was determined by NMR spectra.In this situation,the active moiety{PO_(4)[WO(O_(2))_(2)]_(4)}_(3)-in phase-transfer catalytic system can break into some unidentified species with low W/P ratio with the presence of epoxides.This work will be beneficial for the design of new PTCs in alkene epoxidation in fine chemical industry.
基金supported by Guangdong Science and Technology Planning Project(2015A020216002)Guangdong Natural Science Foundation(2014A030313259)the National Natural Science Foundation of China(21543014,21173086,U1301245)~~
文摘The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variations in the catalyst structure and morphology with pH values were characterized by X-ray power diffraction,nitrogen adsorption-desorption analysis,transmission electron microscopy and X-ray photoelectron spectroscopy.As the pH value applied during the initial synthesis,the resulting Cu-KIT-6_x exhibited different structural,textural and surface characteristics,especially in terms of specific copper species and copper content At a pH value of 3.78,approximately 4.6 wt%copper（Ⅱ） was successfully incorporated into the framework of the initial KIT-6,in the form of-Cu-O-Si- groups.The catalytic performance of each catalyst was evaluated by following the epoxidation of styrene,employing tert-butyl hydroperoxide as the oxidant and CH_3CN as the solvent.A significant styrene conversion of 43.5%with 86.6%selectivity for the desired styrene epoxide was obtained over the Cu-KIT-63.78.A higher Cu content,an ordered cubic laid mesoporous architecture and various specific textural characteristics all combined to endow the Cu-KIT-63.78 with high catalytic activity and good stability.
文摘The polymerization of styrene is monitored by pyrene excimer formation. The ratio of monomer to excimer intensities ( I m/ I e) of pyrene increases as polymerization proceeds. The increase of I m/ I e is ascribed to the increase of microviscosity surrounding the probes forming excimer during polymerization. The linear relationship between the changing rate of I m/ I e and the polymerization rate of styrene is obtained. Therefore, I m/ I e may be used to monitor the progress of the polymerization of styrene.
