The interconversion between the two distinct isomers of methyl vinyl ether （MVE）, the formation of the primary ozonides from O3-initated reactions of MVE, the transformation between the primary ozonides, and the sub...The interconversion between the two distinct isomers of methyl vinyl ether （MVE）, the formation of the primary ozonides from O3-initated reactions of MVE, the transformation between the primary ozonides, and the subsequent fragmentation were studied using quantum chemical methods at the BHandHLYP/6311＋＋G（d,p） level of theory for optimized geometries and frequency calculations and at the QCISD/631G（d,p） level for the single point energy calculations. The rate coefficients were calculated for the temperature range 280-440 K by using the canonical transition state theory （TST）. For ozone addition to MVE, there are two different possibilities discussed on the basis of two different possible orientations for ozone attack. The results of the theoretical study indicate that although the synperiplanar-MVE is 7.11 kJ/mol more stable than the antiperiplanar-MVE, the antiperiplanar-MVE plays a more important role in formation of the primary ozonides because the primary ozonides formed from the ozone addition antiperiplanar-MVE are more stable and the energy barriers corresponding to transition states are lower. The intereonversion between the primary ozonides formed from the ozone addition to antiperiplanar-MVE is the most accessible compared with the transformations between other primary ozonides. The cleavage of the primary ozonides mainly leads to the formation of the CH2OO, which is in agreement with the experimental estimates. The calculated overall rate constant for the ozone-initiated reactions is 4.8× 10^-17 cm^3/（molecule.s） at 298.15 K, which agrees with the experimental value for ethyl vinyl ether.展开更多
Polymerization of isobutyl vinyl ether(IBVE)has been studied with mononuclear half-titanocene,CpTiCl_3[1]and dinuclear half-titanocenes,[(C_5H_4)_2(CH_2)_n][(TiCl_3)_2][2(n=3),3(n=6)],and[(C_5H_4)_2(CH_2)_n[(TiCl_2OR_...Polymerization of isobutyl vinyl ether(IBVE)has been studied with mononuclear half-titanocene,CpTiCl_3[1]and dinuclear half-titanocenes,[(C_5H_4)_2(CH_2)_n][(TiCl_3)_2][2(n=3),3(n=6)],and[(C_5H_4)_2(CH_2)_n[(TiCl_2OR_2](R=2,6- diisopropylphenoxyl)[4(n=3),5(n=6)],in the presence of methyl aluminoxanes(MAO)as cocatalyst in methylene chloride.The influences of the length of polymethylene brigde and the substitution of aryloxy group at the metal center have been investigated at three polymerization temperature(...展开更多
A mild, one-pot procedure for the synthesis of vinyl ethers in good yields from 2-hydroxyalkyl phenyl selenides with primary or secondary organic halides has been developed.
A new comblike polymer host for polymer electrolyte was synthesized by reacting monomethyl ether of poly(ethylene glycol) with poly(vinyl methyl ether-alt-maleic anhydride) and endcapping the residual carboxylic acid ...A new comblike polymer host for polymer electrolyte was synthesized by reacting monomethyl ether of poly(ethylene glycol) with poly(vinyl methyl ether-alt-maleic anhydride) and endcapping the residual carboxylic acid with methanol. Butanone was selected as a solvent for the esterification in order to obtain a completely soluble product. The synthesis process was traced through by LR. Compared with the model compounds, the presumed structure of this comblike polymer has been proved to be valid by C-13 NMR The comb polymer is a white rubbery solid. It can be dissolved in butanone and THF, and manifests good film forming ability.展开更多
文摘The interconversion between the two distinct isomers of methyl vinyl ether （MVE）, the formation of the primary ozonides from O3-initated reactions of MVE, the transformation between the primary ozonides, and the subsequent fragmentation were studied using quantum chemical methods at the BHandHLYP/6311＋＋G（d,p） level of theory for optimized geometries and frequency calculations and at the QCISD/631G（d,p） level for the single point energy calculations. The rate coefficients were calculated for the temperature range 280-440 K by using the canonical transition state theory （TST）. For ozone addition to MVE, there are two different possibilities discussed on the basis of two different possible orientations for ozone attack. The results of the theoretical study indicate that although the synperiplanar-MVE is 7.11 kJ/mol more stable than the antiperiplanar-MVE, the antiperiplanar-MVE plays a more important role in formation of the primary ozonides because the primary ozonides formed from the ozone addition antiperiplanar-MVE are more stable and the energy barriers corresponding to transition states are lower. The intereonversion between the primary ozonides formed from the ozone addition to antiperiplanar-MVE is the most accessible compared with the transformations between other primary ozonides. The cleavage of the primary ozonides mainly leads to the formation of the CH2OO, which is in agreement with the experimental estimates. The calculated overall rate constant for the ozone-initiated reactions is 4.8× 10^-17 cm^3/（molecule.s） at 298.15 K, which agrees with the experimental value for ethyl vinyl ether.
基金the Korea Ministry of Commerce,Industry,and Energy(Grant RTI04-01-04,Regional Technology Innovation Program).
文摘Polymerization of isobutyl vinyl ether(IBVE)has been studied with mononuclear half-titanocene,CpTiCl_3[1]and dinuclear half-titanocenes,[(C_5H_4)_2(CH_2)_n][(TiCl_3)_2][2(n=3),3(n=6)],and[(C_5H_4)_2(CH_2)_n[(TiCl_2OR_2](R=2,6- diisopropylphenoxyl)[4(n=3),5(n=6)],in the presence of methyl aluminoxanes(MAO)as cocatalyst in methylene chloride.The influences of the length of polymethylene brigde and the substitution of aryloxy group at the metal center have been investigated at three polymerization temperature(...
基金the Natural Science Foundation of Jiangxi Province(No.0420017)for financial support
文摘A mild, one-pot procedure for the synthesis of vinyl ethers in good yields from 2-hydroxyalkyl phenyl selenides with primary or secondary organic halides has been developed.
文摘A new comblike polymer host for polymer electrolyte was synthesized by reacting monomethyl ether of poly(ethylene glycol) with poly(vinyl methyl ether-alt-maleic anhydride) and endcapping the residual carboxylic acid with methanol. Butanone was selected as a solvent for the esterification in order to obtain a completely soluble product. The synthesis process was traced through by LR. Compared with the model compounds, the presumed structure of this comblike polymer has been proved to be valid by C-13 NMR The comb polymer is a white rubbery solid. It can be dissolved in butanone and THF, and manifests good film forming ability.
