In the field of highly integrated printed circuit board （PCB）, the heat resistant substrate with low water absorption is very important material. To get the resin composition for the high functional substrate materi...In the field of highly integrated printed circuit board （PCB）, the heat resistant substrate with low water absorption is very important material. To get the resin composition for the high functional substrate material with low moisture absorption and high glass transition temperature （Tg） simultaneously, a fluorenyl ＂Cardo＂ epoxy was incorporated into novolac cyanate ester resin. As an optimum curing agent for the fiuorenyl epoxy, methyl nadic anhydride （MNA） was selected. Silica powders as fillers were added into the resin composition. The partial replacement of the cyanate ester resin with the fluorenyl epoxy could reduce the moisture absorption with keeping high glass transition temperature over 300 ℃. The laminate, which was fabricated from prepregs made with 40 wt% silica-filled resin composition and glass fabric, showed high Tg of 317 ℃ and low moisture absorption of 0.57%.展开更多
Four C_1-symmetric ansa-metallocene complexes, C_2H_4(Ind)(2,7-~tBu_2-Flu)ZrCl_2(4), C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)ZrCl_2(5),C_2H_4(3-Bn-Ind)(3,6-~tBu_2-Flu)ZrCl_2(6), and C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)HfCl_2(7), ...Four C_1-symmetric ansa-metallocene complexes, C_2H_4(Ind)(2,7-~tBu_2-Flu)ZrCl_2(4), C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)ZrCl_2(5),C_2H_4(3-Bn-Ind)(3,6-~tBu_2-Flu)ZrCl_2(6), and C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)HfCl_2(7), were synthesized and characterized. The structures of complexes 4, 5, and 7 were further determined via X-ray diffraction studies. Upon activation with modified methylaluminoxane(MMAO) or Al^iBu_3/[Ph_3C][B(C_6F_5)_4](TIBA/TrB), most of these complexes showed high efficiency in catalyzing propylene oligomerization/polymerization to afford products dominantly with allyl terminals via selective β-methyl transfer(β-Me transfer). The introduction of 3-benzyl group on the indenyl ring of the complexes was found to be crucial in enabling highly selective β-Me transfer during the polymerization process, leading to selectivities up to 89% obtained by zirconocene complexes 5 and 6, and up to 91% obtained by hafnocene complex 7. Detailed chain-end analysis by ~1H-NMR, ^(13)C-NMR, and MALDI-TOF mass spectroscopy revealed that the allyl chain-ends of the polymeric products resulted from a selective β-Me transfer process after two successively primary insertions of the monomer. Further studies concerning the dependence of chain release selectivity as well as the molecular weight of products on monomer concentration suggested that both β-Me transfer(major) and β-hydrogen transfer(β-H transfer)(minor) mediated by 5/MMAO and 6/MMAO systems may mainly operate in a bimolecular pathway.展开更多
Three novel triarylamine dyes（AFL1-AFL3） containing fluorenyl and the biphenyl moieties have been designed and synthesized for application in dye-sensitized solar cells.The light-harvesting capabilities and photovol...Three novel triarylamine dyes（AFL1-AFL3） containing fluorenyl and the biphenyl moieties have been designed and synthesized for application in dye-sensitized solar cells.The light-harvesting capabilities and photovoltaic performance of these dyes were investigated systematically through comparison of different π-bridges.The dye with a furan linker exhibited a higher open-circuit voltage（VOC） and monochromatic incident photon-to-current conversion efficiency（IPCE） compared to thiophene and benzene linker.Thus,AFL3 containing a furan linker exhibited the maximum overall conversion efficiency of 5.81%（VOC = 760 mV,JSC = 11.36 mA cm^-2 and ff=0.68） under standard global AM 1.5 G solar condition.展开更多
首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化...首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化为溴甲基;然后,通过4-羟基苯磺酸钠的SN2亲核取代制得具有不同离子交换容量的磺化聚芴醚酮(SPFEK-x);最后,通过溶液浇铸法成膜并酸化,制得新型低成本质子交换膜(PEMs)。采用^(1)HNMR、FTIR、TGA对其进行了表征,并对其性能进行了测试。结果表明,SPFEK-40膜具有较高的质子传导率及离子选择性、较低的钒离子渗透率及面电阻,综合性能优异。以SPFEK-40膜组装的全钒液流电池(VRFB)在电流密度为80 m A/cm^(2)时的能量效率为88.2%,高于以Nafion 212膜组装的VRFB的84.8%。此外,以SPFEK-40膜组装的VRFB在30次循环后放电容量保持率为84.3%,远高于以Nafion 212膜组装的VRFB(66.1%)。该合成路线的原料来源广泛,价格低廉,不涉及危险的磺化反应,易于工业放大。制得的SPFEK-x均具有良好的机械性能和氧化稳定性。展开更多
A new fluorescent sensor consisted of fluorenyl and dioxotetraaza unit, dimethyl-6-(9-fluorenyl)-1,4,8,11-tetraazaundencane-5,7-dione (L), was synthesize fluorescent sensor for transition metal ions in aqueous solution.
文摘In the field of highly integrated printed circuit board （PCB）, the heat resistant substrate with low water absorption is very important material. To get the resin composition for the high functional substrate material with low moisture absorption and high glass transition temperature （Tg） simultaneously, a fluorenyl ＂Cardo＂ epoxy was incorporated into novolac cyanate ester resin. As an optimum curing agent for the fiuorenyl epoxy, methyl nadic anhydride （MNA） was selected. Silica powders as fillers were added into the resin composition. The partial replacement of the cyanate ester resin with the fluorenyl epoxy could reduce the moisture absorption with keeping high glass transition temperature over 300 ℃. The laminate, which was fabricated from prepregs made with 40 wt% silica-filled resin composition and glass fabric, showed high Tg of 317 ℃ and low moisture absorption of 0.57%.
基金financially supported by the National Natural Science Foundation of China (No. 21274041)the Key Project of Chinese Ministry of Education (No. 109064)the Fundamental Research Funds for the Central Universities (No. WK1214048)
文摘Four C_1-symmetric ansa-metallocene complexes, C_2H_4(Ind)(2,7-~tBu_2-Flu)ZrCl_2(4), C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)ZrCl_2(5),C_2H_4(3-Bn-Ind)(3,6-~tBu_2-Flu)ZrCl_2(6), and C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)HfCl_2(7), were synthesized and characterized. The structures of complexes 4, 5, and 7 were further determined via X-ray diffraction studies. Upon activation with modified methylaluminoxane(MMAO) or Al^iBu_3/[Ph_3C][B(C_6F_5)_4](TIBA/TrB), most of these complexes showed high efficiency in catalyzing propylene oligomerization/polymerization to afford products dominantly with allyl terminals via selective β-methyl transfer(β-Me transfer). The introduction of 3-benzyl group on the indenyl ring of the complexes was found to be crucial in enabling highly selective β-Me transfer during the polymerization process, leading to selectivities up to 89% obtained by zirconocene complexes 5 and 6, and up to 91% obtained by hafnocene complex 7. Detailed chain-end analysis by ~1H-NMR, ^(13)C-NMR, and MALDI-TOF mass spectroscopy revealed that the allyl chain-ends of the polymeric products resulted from a selective β-Me transfer process after two successively primary insertions of the monomer. Further studies concerning the dependence of chain release selectivity as well as the molecular weight of products on monomer concentration suggested that both β-Me transfer(major) and β-hydrogen transfer(β-H transfer)(minor) mediated by 5/MMAO and 6/MMAO systems may mainly operate in a bimolecular pathway.
基金National Natural Science Foundation of China (No. 21176223)National Natural Science Foundation of China (No. 21406202)Natural Science Foundation of Zhejiang province (No. LY15B020009)
文摘Three novel triarylamine dyes（AFL1-AFL3） containing fluorenyl and the biphenyl moieties have been designed and synthesized for application in dye-sensitized solar cells.The light-harvesting capabilities and photovoltaic performance of these dyes were investigated systematically through comparison of different π-bridges.The dye with a furan linker exhibited a higher open-circuit voltage（VOC） and monochromatic incident photon-to-current conversion efficiency（IPCE） compared to thiophene and benzene linker.Thus,AFL3 containing a furan linker exhibited the maximum overall conversion efficiency of 5.81%（VOC = 760 mV,JSC = 11.36 mA cm^-2 and ff=0.68） under standard global AM 1.5 G solar condition.
文摘首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化为溴甲基;然后,通过4-羟基苯磺酸钠的SN2亲核取代制得具有不同离子交换容量的磺化聚芴醚酮(SPFEK-x);最后,通过溶液浇铸法成膜并酸化,制得新型低成本质子交换膜(PEMs)。采用^(1)HNMR、FTIR、TGA对其进行了表征,并对其性能进行了测试。结果表明,SPFEK-40膜具有较高的质子传导率及离子选择性、较低的钒离子渗透率及面电阻,综合性能优异。以SPFEK-40膜组装的全钒液流电池(VRFB)在电流密度为80 m A/cm^(2)时的能量效率为88.2%,高于以Nafion 212膜组装的VRFB的84.8%。此外,以SPFEK-40膜组装的VRFB在30次循环后放电容量保持率为84.3%,远高于以Nafion 212膜组装的VRFB(66.1%)。该合成路线的原料来源广泛,价格低廉,不涉及危险的磺化反应,易于工业放大。制得的SPFEK-x均具有良好的机械性能和氧化稳定性。
文摘A new fluorescent sensor consisted of fluorenyl and dioxotetraaza unit, dimethyl-6-(9-fluorenyl)-1,4,8,11-tetraazaundencane-5,7-dione (L), was synthesize fluorescent sensor for transition metal ions in aqueous solution.
