The branching generation during the free radical copolymerization of chain transfer monomer p-vinyl benzene sulfonyl chloride （VBSC） with styrene was investigated by a simple mathematic model. Chain transfer constan...The branching generation during the free radical copolymerization of chain transfer monomer p-vinyl benzene sulfonyl chloride （VBSC） with styrene was investigated by a simple mathematic model. Chain transfer constant of VBSC was determined to be around 0.3 by fitting the 1H-NMR monitored experimental results with a mathematic model. According to the theoretical analysis, the obtained poIy（VBSC） and its copolymers were substantiated to have a grafting-like main chain with residual pendent sulfonyl chloride groups after consuming most of the vinyl groups. The copolymerization results of VBSC with styrene at varied feed ratios demonstrated that conversion of sulfonyl chloride groups was lower than that of the monomer, which was in agreement with the theoretical results. The glass transition temperature, number average molecular weight and distribution of those obtained polymers were primarily investigated. Comparing with other chain transfer monomers, VBSC has a chain transfer constant much closer to unity therefore a more branched polymer is expected. Additionally, the branched polystyrene with residual sulfonyl chloride groups is hopefully to be further used as ATRP macro- initiators or reactive intermediates to synthesize functional polymers with complex structure.展开更多
We have demonstrated a facile approach for the low-temperature synthesis of crystalline inorganic/metallic nanocrystal-halloysite composite nanotubes by employing the bulk controlled synthesis of inorganic/metallic na...We have demonstrated a facile approach for the low-temperature synthesis of crystalline inorganic/metallic nanocrystal-halloysite composite nanotubes by employing the bulk controlled synthesis of inorganic/metallic nanocrystals on halloysite nanotubes.The halloysite clay nanotubes can adsorb the target precursor and induce inorganic/metallic nanocrystals to grow in situ.The crystalline phase and morphology of the composite clay nanotubes is tunable.By simply tuning the acidity of the titania sol,the crystalline titania-clay nanotubes with tunable crystalline phases of anatase,a mixture of anatase and rutile or rutile are achieved.The approach is general and has been extended to synthesize the representative perovskite oxide(barium and strontium titanate)-halloysite composite nanotubes.Metallic nickel nanocrystal can also be grown on the surface of halloysite nanotubes at low temperature.The traditional thermal treatment for crystallite transformation is not required,thus intact contour of halloysite nanotubes and the crystallinity structure of halloysite nanotubes can be guaranteed.The combined properties from inorganic/metallic nanocrystal(high refractive index,high dielectric constant and catalytic ability)and the halloysite clay nanotubes are promising for applications such as photonic crystals,high-k-gate dielectrics,photocatalysis and purification.展开更多
基金supported by the National Natural Science Foundation of China(No.51003091)the Education Research Foundation of Yunnan Province(No.2010Y240)+1 种基金the Research Foundation of Yunnan University(No.2009B06Q)the Backbone Teacher Training Program of Yunnan University(No.21132014)
文摘The branching generation during the free radical copolymerization of chain transfer monomer p-vinyl benzene sulfonyl chloride （VBSC） with styrene was investigated by a simple mathematic model. Chain transfer constant of VBSC was determined to be around 0.3 by fitting the 1H-NMR monitored experimental results with a mathematic model. According to the theoretical analysis, the obtained poIy（VBSC） and its copolymers were substantiated to have a grafting-like main chain with residual pendent sulfonyl chloride groups after consuming most of the vinyl groups. The copolymerization results of VBSC with styrene at varied feed ratios demonstrated that conversion of sulfonyl chloride groups was lower than that of the monomer, which was in agreement with the theoretical results. The glass transition temperature, number average molecular weight and distribution of those obtained polymers were primarily investigated. Comparing with other chain transfer monomers, VBSC has a chain transfer constant much closer to unity therefore a more branched polymer is expected. Additionally, the branched polystyrene with residual sulfonyl chloride groups is hopefully to be further used as ATRP macro- initiators or reactive intermediates to synthesize functional polymers with complex structure.
基金National Natural Science Foundation of China(No.51003091)the Applied Basic Foundation of Yunnan Province(No.2013FB002)+2 种基金the Education Research Foundation of Yunnan Province(Nos.2013Y361,2010Y240)the Research Foundation of Yunnan University(No.2009B06Q)the Backbone Teacher Training Program of Yunnan University(No.XT412003).
文摘We have demonstrated a facile approach for the low-temperature synthesis of crystalline inorganic/metallic nanocrystal-halloysite composite nanotubes by employing the bulk controlled synthesis of inorganic/metallic nanocrystals on halloysite nanotubes.The halloysite clay nanotubes can adsorb the target precursor and induce inorganic/metallic nanocrystals to grow in situ.The crystalline phase and morphology of the composite clay nanotubes is tunable.By simply tuning the acidity of the titania sol,the crystalline titania-clay nanotubes with tunable crystalline phases of anatase,a mixture of anatase and rutile or rutile are achieved.The approach is general and has been extended to synthesize the representative perovskite oxide(barium and strontium titanate)-halloysite composite nanotubes.Metallic nickel nanocrystal can also be grown on the surface of halloysite nanotubes at low temperature.The traditional thermal treatment for crystallite transformation is not required,thus intact contour of halloysite nanotubes and the crystallinity structure of halloysite nanotubes can be guaranteed.The combined properties from inorganic/metallic nanocrystal(high refractive index,high dielectric constant and catalytic ability)and the halloysite clay nanotubes are promising for applications such as photonic crystals,high-k-gate dielectrics,photocatalysis and purification.
