The silicon-containing poly (amic acid)s were synthesized from bis (3, 4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (4,4'-ODA) in N, N-dimethylacetam...The silicon-containing poly (amic acid)s were synthesized from bis (3, 4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (4,4'-ODA) in N, N-dimethylacetamide (DMAc). The poly (amic acid) films were obtained by solution-cast method from DMAc solutions and thermally converted into transparent, flexible and tough polyimide films. The wide-angle X-ray diffraction diagrams revealed that all the polyimides possessed amorphous character, and the regulation of those polyimides were decreased with the increase of the molar ratio of SIDA to PMDA. Differential scanning calorimeter measurements showed that the introduction of SIDA to polyimide backbone would make glass transition temperature shift to lower temperature. Thermogravimetric analyses indicated that the silicon-containing polyimides lowered decomposition temperature as compared with PMDA/4, 4′-ODA polyimides. However, UV-visible transmission and reflection spectra showed that the optical transparency of silicon-containing polyimide thin films was superior to that of PMDA/4, 4'-ODA polyimide thin films.展开更多
The mechanism of the cycloaddition reaction of forming a silicic bis-heterocyclic compound between singlet dimethylmethylenesilylene （Me2C=Si：） and ethene has been investigated with the CCSD（T）//MP2/6-31G＊ metho...The mechanism of the cycloaddition reaction of forming a silicic bis-heterocyclic compound between singlet dimethylmethylenesilylene （Me2C=Si：） and ethene has been investigated with the CCSD（T）//MP2/6-31G＊ method. From the potential energy profile, it can be predicted that, this reaction has one dominant channel. The presented rule of this dominant channel： the 3p unoccupied orbital of Si in dimethylmethylenesilylene and the π orbital of ethene forming the π→p donor-acceptor bond, resulting in the formation of three-membered ring intermediate （INT1）; INT1 then isomerizes to a four-membered ring silylene （P2）, which is driven by ring-enlargement effect; due to sp3 hybridization of Si atom in P2, P2 further combines with ethene to form a silicic bis-heterocyclic compound.展开更多
The mechanism of the cycloaddition reaction between singlet dimethyl-silylene carbene and acetone has been investigated with density functional theory, From the potential energy profile, it can be predicted that the r...The mechanism of the cycloaddition reaction between singlet dimethyl-silylene carbene and acetone has been investigated with density functional theory, From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The presented rule of this reaction： the [2＋2] cycloaddition effect between the πorbital of dimethyl-silylene carbene and the π orbital of π-bonded compounds leads to the formation of a twisty four-membered ring intermediate and a planar four-membered ring product; The unsaturated property of C atom from carbene in the planar four-membered ring product,resulting in the generation of CH3-transfer product and silicic bis-heterocyclic compound.展开更多
In this study,porous silica with high surface area was prepared through selective leaching of thermally activated chlorite in HCl solution.In the process,chlorite was activated by pre-calcining treatment,then activate...In this study,porous silica with high surface area was prepared through selective leaching of thermally activated chlorite in HCl solution.In the process,chlorite was activated by pre-calcining treatment,then activated components(MgO,Al_(2)O_(3),and Fe_(2)O_(3))were selectively leached by acid solution,resulting in the formation of nanopores in situ.The morphology,structure,surface area and pore-size distribution of the material were characterized by XRD,TG/DSC,^(27)Al MAS NMR,SEM,TEM and N2 adsorption−desorption isotherms.The highest specific surface area(SBET=333 m^(2)/g)was obtained by selectively leaching the 600℃ calcined chlorite from 3 mol/L HCl at 90℃ for 2 h.The pore sizes and specific surface areas can be controlled by calcination and leaching conditions.The ^(27)Al MAS NMR spectra of the samples revealed the relationship between structural transformation and the selective acid leaching properties of thermal-activated chlorite,demonstrating that AlVI transfers into AlV when chlorite changes into activated chlorite during thermal activation,and the coordinations of Al has a significant effect on acid solubility of chlorite.The as-prepared porous silica showed favorable adsorption abilities with capacity of 148.79 mg/g for methylene blue at pH of about 7 and temperature of 25℃,indicating its promising potential in adsorption application.展开更多
文摘The silicon-containing poly (amic acid)s were synthesized from bis (3, 4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (4,4'-ODA) in N, N-dimethylacetamide (DMAc). The poly (amic acid) films were obtained by solution-cast method from DMAc solutions and thermally converted into transparent, flexible and tough polyimide films. The wide-angle X-ray diffraction diagrams revealed that all the polyimides possessed amorphous character, and the regulation of those polyimides were decreased with the increase of the molar ratio of SIDA to PMDA. Differential scanning calorimeter measurements showed that the introduction of SIDA to polyimide backbone would make glass transition temperature shift to lower temperature. Thermogravimetric analyses indicated that the silicon-containing polyimides lowered decomposition temperature as compared with PMDA/4, 4′-ODA polyimides. However, UV-visible transmission and reflection spectra showed that the optical transparency of silicon-containing polyimide thin films was superior to that of PMDA/4, 4'-ODA polyimide thin films.
文摘The mechanism of the cycloaddition reaction of forming a silicic bis-heterocyclic compound between singlet dimethylmethylenesilylene （Me2C=Si：） and ethene has been investigated with the CCSD（T）//MP2/6-31G＊ method. From the potential energy profile, it can be predicted that, this reaction has one dominant channel. The presented rule of this dominant channel： the 3p unoccupied orbital of Si in dimethylmethylenesilylene and the π orbital of ethene forming the π→p donor-acceptor bond, resulting in the formation of three-membered ring intermediate （INT1）; INT1 then isomerizes to a four-membered ring silylene （P2）, which is driven by ring-enlargement effect; due to sp3 hybridization of Si atom in P2, P2 further combines with ethene to form a silicic bis-heterocyclic compound.
文摘The mechanism of the cycloaddition reaction between singlet dimethyl-silylene carbene and acetone has been investigated with density functional theory, From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The presented rule of this reaction： the [2＋2] cycloaddition effect between the πorbital of dimethyl-silylene carbene and the π orbital of π-bonded compounds leads to the formation of a twisty four-membered ring intermediate and a planar four-membered ring product; The unsaturated property of C atom from carbene in the planar four-membered ring product,resulting in the generation of CH3-transfer product and silicic bis-heterocyclic compound.
基金Project(51772153)supported by the National Natural Science Foundation of China。
文摘In this study,porous silica with high surface area was prepared through selective leaching of thermally activated chlorite in HCl solution.In the process,chlorite was activated by pre-calcining treatment,then activated components(MgO,Al_(2)O_(3),and Fe_(2)O_(3))were selectively leached by acid solution,resulting in the formation of nanopores in situ.The morphology,structure,surface area and pore-size distribution of the material were characterized by XRD,TG/DSC,^(27)Al MAS NMR,SEM,TEM and N2 adsorption−desorption isotherms.The highest specific surface area(SBET=333 m^(2)/g)was obtained by selectively leaching the 600℃ calcined chlorite from 3 mol/L HCl at 90℃ for 2 h.The pore sizes and specific surface areas can be controlled by calcination and leaching conditions.The ^(27)Al MAS NMR spectra of the samples revealed the relationship between structural transformation and the selective acid leaching properties of thermal-activated chlorite,demonstrating that AlVI transfers into AlV when chlorite changes into activated chlorite during thermal activation,and the coordinations of Al has a significant effect on acid solubility of chlorite.The as-prepared porous silica showed favorable adsorption abilities with capacity of 148.79 mg/g for methylene blue at pH of about 7 and temperature of 25℃,indicating its promising potential in adsorption application.
