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
To avoid the damage to catalytic system in ATRP by the carboxyl groups in vinyl benzoic acid, a well defined poly( p vinyl benzoic acid) was synthesized via ATRP in the tertiary butyl ester form. The ATRP of t butyl p...To avoid the damage to catalytic system in ATRP by the carboxyl groups in vinyl benzoic acid, a well defined poly( p vinyl benzoic acid) was synthesized via ATRP in the tertiary butyl ester form. The ATRP of t butyl p vinyl benzoate ( t BVB) was studied kinetically. The results showed that t BVB can be polymerized in a controlled way by ATRP. It was found that the polymerization rate of t BVB is much faster than that of St, meaning that the electron withdrawing ester group affects the polymerization obviously. Well defined diblock copolymers of St and t BVB were prepared by using bromo terminated PBVBs as macroinitiators via ATRP. After removal of the t butyl group by hydrolysis, well defined amphiphilic diblock copolymers of styrene and p vinyl benzoic acid (PSt b PBVA) were obtained.展开更多
The photoconductive characteristic of the inorganic/organic hybridized polymer system is reported, in which a novel bi-functional photorefractive (PR) poly(N-vinyl)-3-[p-nitrophenylazo]carbazole (PVNPAK) serves as a p...The photoconductive characteristic of the inorganic/organic hybridized polymer system is reported, in which a novel bi-functional photorefractive (PR) poly(N-vinyl)-3-[p-nitrophenylazo]carbazole (PVNPAK) serves as a polymeric charge-transporting and second-order nonliner optical matrix and quantum dots composed of surface passivated cadmium sulfide serve as a charge-generation sensitizer. The hybrid PVNPAK/CdS-nanoparticles polymer composites with different mass ratio of CdS to PVNPAK were prepared. The generation of photocurrent on illumination and photoconductive properties of the PVNPAK/CdS-nanoparticles polymer composites were studied. The results show that the addition of CdS nanoparticle as a photosensitizer can enhance the photoconductivity of the PVNPAK significantly because of the properties of the high quantum efficiency of photosensitization and high charge transport to conducting polymer.展开更多
We have analyzed the photorefractive（PR） effect of a polymer composite was reported which combines a novel bi-functional poly（N-vinyl）-3-[p-nitrophenylazo]carbazolyl（PVNPAK） and 2,4,7-trinitro-9-fluorenone（TNF...We have analyzed the photorefractive（PR） effect of a polymer composite was reported which combines a novel bi-functional poly（N-vinyl）-3-[p-nitrophenylazo]carbazolyl（PVNPAK） and 2,4,7-trinitro-9-fluorenone（TNF）. PVNPAK was synthesized by a post-azo-coupling reaction, with an azo derivative as the electrooptic chromophore and carbazolyl as photoconductive moiety. The asymmetric two-beam coupling gain of 13.9 cm-1 and diffraction efficiency of 1.2% for poled polymer film fabricated using a corona poling are obtained at the wavelength of 647.1 nm, confirming photorefractivity. We interpreted this result as the orientational enhancement, in which the spatial charge field may enhance the modulated orientation of the azobenzen chromophore. It is unexpected that the photorefractive gain of 9.5 cm-1 for the unpoled polymer film also was observed without external field in two-beam coupling（TBC） experiment. This phenomenon is attributed to a light-induced orientational grating when the azobenzene groups are illuminated by polarized light.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.
文摘To avoid the damage to catalytic system in ATRP by the carboxyl groups in vinyl benzoic acid, a well defined poly( p vinyl benzoic acid) was synthesized via ATRP in the tertiary butyl ester form. The ATRP of t butyl p vinyl benzoate ( t BVB) was studied kinetically. The results showed that t BVB can be polymerized in a controlled way by ATRP. It was found that the polymerization rate of t BVB is much faster than that of St, meaning that the electron withdrawing ester group affects the polymerization obviously. Well defined diblock copolymers of St and t BVB were prepared by using bromo terminated PBVBs as macroinitiators via ATRP. After removal of the t butyl group by hydrolysis, well defined amphiphilic diblock copolymers of styrene and p vinyl benzoic acid (PSt b PBVA) were obtained.
基金Project(60537050) supported by the National Nature Science Foundation of China Project supported by the Opening Fund of Key Laboratory of Nonferrous Materials and Processing Technology.
文摘The photoconductive characteristic of the inorganic/organic hybridized polymer system is reported, in which a novel bi-functional photorefractive (PR) poly(N-vinyl)-3-[p-nitrophenylazo]carbazole (PVNPAK) serves as a polymeric charge-transporting and second-order nonliner optical matrix and quantum dots composed of surface passivated cadmium sulfide serve as a charge-generation sensitizer. The hybrid PVNPAK/CdS-nanoparticles polymer composites with different mass ratio of CdS to PVNPAK were prepared. The generation of photocurrent on illumination and photoconductive properties of the PVNPAK/CdS-nanoparticles polymer composites were studied. The results show that the addition of CdS nanoparticle as a photosensitizer can enhance the photoconductivity of the PVNPAK significantly because of the properties of the high quantum efficiency of photosensitization and high charge transport to conducting polymer.
基金Funded by the National Natural Science Foundation of China(No.51303115)
文摘We have analyzed the photorefractive（PR） effect of a polymer composite was reported which combines a novel bi-functional poly（N-vinyl）-3-[p-nitrophenylazo]carbazolyl（PVNPAK） and 2,4,7-trinitro-9-fluorenone（TNF）. PVNPAK was synthesized by a post-azo-coupling reaction, with an azo derivative as the electrooptic chromophore and carbazolyl as photoconductive moiety. The asymmetric two-beam coupling gain of 13.9 cm-1 and diffraction efficiency of 1.2% for poled polymer film fabricated using a corona poling are obtained at the wavelength of 647.1 nm, confirming photorefractivity. We interpreted this result as the orientational enhancement, in which the spatial charge field may enhance the modulated orientation of the azobenzen chromophore. It is unexpected that the photorefractive gain of 9.5 cm-1 for the unpoled polymer film also was observed without external field in two-beam coupling（TBC） experiment. This phenomenon is attributed to a light-induced orientational grating when the azobenzene groups are illuminated by polarized light.
