The synthesis of rod-coil diblock copolymers was achieved for the first time by TEMPO-mediated 'living' free radical polymerization of styrene and 2,5-bis [(4-methoxyphenyl)oxycarbonyl] styrene(MPCS). The blo...The synthesis of rod-coil diblock copolymers was achieved for the first time by TEMPO-mediated 'living' free radical polymerization of styrene and 2,5-bis [(4-methoxyphenyl)oxycarbonyl] styrene(MPCS). The block architecture of the two diblock copolymers thus prepared, MPCS-b-St(5400/2400) and MPCS-b-St(10800/8700), was confirmed by GPC, DSC studies and the formation of multimolecular micelles. (Author abstract) 10 Refs.展开更多
The first TEMPO-mediated 'living' free radical polymerization of liquid crystalline monomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS), was carried out at 130 degrees C with BPO as an initiator. The...The first TEMPO-mediated 'living' free radical polymerization of liquid crystalline monomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS), was carried out at 130 degrees C with BPO as an initiator. The molecular weight of the polymer can be varied from rather low values to high values while maintaining narrow polydispersity. It was observed that the polymerization of MPCS proceeded much faster than that of styrene. A tentative explanation for this fast polymerization was suggested.展开更多
Poly{2, 5-bis[(p-methoxyphenyl)oxycarbonyl]styrene} was successfully synthesized. This new polymer has a structure characteristic of mesogen-jacketed liquid cyrstalline polymers (MJLCPs) and does form a liquid crystal...Poly{2, 5-bis[(p-methoxyphenyl)oxycarbonyl]styrene} was successfully synthesized. This new polymer has a structure characteristic of mesogen-jacketed liquid cyrstalline polymers (MJLCPs) and does form a liquid crystal phase above its glass transition. It thus became the starting member of a new series of MJLCPs. The synthesis of the polymer as well as the liquid crystalline properties of the polymer and its monomer was discussed. A brief comparison of the new monomer and polymer with some previously reported counterparts was also included.展开更多
Mesogen-jacketed liquid crystalline polymer （MJLCP） has attracted great attention because of its rigid conformation, facile synthesis, and structural controllability. In this feature article, the self-assembly of MJ...Mesogen-jacketed liquid crystalline polymer （MJLCP） has attracted great attention because of its rigid conformation, facile synthesis, and structural controllability. In this feature article, the self-assembly of MJLCP-based block copolymers （BCPs） is briefly reviewed, especially the nanostructures of rod-coil diblock copolymers （diBCPs）, rod-rod diBCPs, and triblock copolymers. In addition, the properties of the self-assembled BCPs are also summarized, including their applications as liquid crystalline thermoplastic elastomers and solid polymer electrolytes. The article also discusses the major challenges and future directions in the study of MJLCP-based BCPs.展开更多
The effects of mesogen-jacketed liquid crystalline polymer poly(dipropyl vinylterephthalate)(PDPVT) on the mechanical and thermal properties of diglycidyl ether of bisphenol-A(DGEBA) epoxy resin were investigated by i...The effects of mesogen-jacketed liquid crystalline polymer poly(dipropyl vinylterephthalate)(PDPVT) on the mechanical and thermal properties of diglycidyl ether of bisphenol-A(DGEBA) epoxy resin were investigated by impact test, tensile test and thermogravimetric analysis(TGA). The mechanism underlying the enhancement of mechanical properties of epoxy resin was studied using 1D wide-angle X-ray diffraction(WAXD) and scanning electron microscope(SEM). It was found that the mechanical properties of 1 wt%–5 wt% PDPVT/DGEBA composites were significantly improved compared to neat epoxy resin. Especially, the epoxy resin with 3 wt% PDPVT had the greatest increase in mechanical properties, with the impact strength, tensile strength and elongation while breaking increased by 87%, 59% and 174%, respectively. The increased mechanical strength was due to the fact that PDPVT maintained liquid crystalline phase in cured PDPVT/DGEBA composites, which would blunt the crack tip and prevent crack propagation. Moreover, PDPVT had slight effect on the thermal stability properties of epoxy resin.展开更多
Some new mesogen-jacketed liquid crystalline polymers (MJLCP) with polymer backbones, spacers, and mesogenic units of different structures were synthesized by radical polymerization. The mesomorphic behavior of these ...Some new mesogen-jacketed liquid crystalline polymers (MJLCP) with polymer backbones, spacers, and mesogenic units of different structures were synthesized by radical polymerization. The mesomorphic behavior of these polymers was examined using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Their liquid crystallinity is influenced by the variation of polymer backbone, spacer, mesogenic unit and its terminal groups. The results show that 1) a more flexible polymer main-chain is more favorable to the formation of a liquid crystal phase, while 2) a flexible spacer will decrease the 'Jacket Effect' and the liquid crystallinity and 3) a subtle modification of the terminal groups on the mesogenic unit may also have a significant influence on properties of the polymers.展开更多
New liquid crystalline monomer, 2,5-bis[(4'-methoxyphenoxy)carbonyl]phenyl acrylate was successfully synthesized. Polyacrylate with laterally attached mesogens via ei;ter linkage was also derived. This polymer for...New liquid crystalline monomer, 2,5-bis[(4'-methoxyphenoxy)carbonyl]phenyl acrylate was successfully synthesized. Polyacrylate with laterally attached mesogens via ei;ter linkage was also derived. This polymer forms an enantiotropic liquid crystal phase while its monomer exhibits a metastable nematic phase with respect to the crystalline state. However, its liquid crystallinity is very low as compared to that of poly{2,5-bis[(4'-methoxyphenoxy)carbonyl]-styrene}.展开更多
A series of poly{2,5-bis[(4-butoxyphenyl)-oxycarbonyl]styrenes}(PBPCS)with low mo-lecular weight distribution was synthesized by atom transfer radical polymerization(ATRP).The me-somorphic properties were investigated...A series of poly{2,5-bis[(4-butoxyphenyl)-oxycarbonyl]styrenes}(PBPCS)with low mo-lecular weight distribution was synthesized by atom transfer radical polymerization(ATRP).The me-somorphic properties were investigated by differential scanning calorimetry(DSC),polarizing optical microscopy(POM)and rheometer.PBPCS showed the phase transition from isotropic into liquid crystal(LC)phase,and the LC phase formed at high temperature and disappeared in the subsequent cooling procedure.Using the WAXD fiber pattern,the phase structure of the PBPCS at higher tem-perature showed hexagonal columnar nematic phase.Experimental results demonstrated that the driving force of the entropy is an important factor during the unusual LC phase formation of PBPCS.展开更多
A mesogen-jacketed liquid crystal polymer,poly{2,5 -bis［(4′-hexyloxyphenyl)oxycarbonyl］styrene}(PHPCS),with number-average d molecular weight of 1.28×１０5 and polydispersity of 1.48 was prepared vi a 2,2,6,6 ...A mesogen-jacketed liquid crystal polymer,poly{2,5 -bis［(4′-hexyloxyphenyl)oxycarbonyl］styrene}(PHPCS),with number-average d molecular weight of 1.28×１０5 and polydispersity of 1.48 was prepared vi a 2,2,6,6 -tetramethyl-piperidinyloxy mediated free radical polymerization.The thermotr opic behavior was studied by a combination of differential scanning calorimetry, thermogravimetry,polarized optical microscope and wide-angle X-ray diffracti on.PHPCS was not crystalline over the entire temperature region studied.On hea ting,PHPCS first became an isotropic melt at glass transition temperature (T g) and then a mesophase at temperatures much higher than T g.On subseq uent cooling,the formed ordered phase disappeared above T g.Contrary to t heoretical predictions and previous experimental observations,the transition fr om isotropic melt to liquid crystalline phase was an endothermic process and th e order-disorder transition took place with concurrence of heat release.展开更多
A series of monomers {2,5-bis[(5-alkyl-phenyl)-1,3,4-oxadiazole] styrene}(BOXE) were designed and synthesized.By radical polymerization initiated BPO with a novel series of mesogen-jacketed polymers containing 1,3,4-o...A series of monomers {2,5-bis[(5-alkyl-phenyl)-1,3,4-oxadiazole] styrene}(BOXE) were designed and synthesized.By radical polymerization initiated BPO with a novel series of mesogen-jacketed polymers containing 1,3,4-oxadiazole were prepared.Molecular weight and molecular weight distribution of polymers were measured by GPC.The glass transition temperature (T_g) and thermal stability of polymers were studied by DSC and TGA.The results indicate that these polymers have good thermal stability.These liquid crystal polymers have well defined structure,and possess special photo-electronic properties.展开更多
It is reported report herein the synthesis and characterization of a new mesogen-jacketed polymer containing an electron deficient oxadiazole unit __ poly{2,5-bis[(5-tert-butylphenyl)-1,3,4-oxadiazole]styrene} (BBPOS)...It is reported report herein the synthesis and characterization of a new mesogen-jacketed polymer containing an electron deficient oxadiazole unit __ poly{2,5-bis[(5-tert-butylphenyl)-1,3,4-oxadiazole]styrene} (BBPOS).BBPOS can be dissolved in THE,CHCl-3,xylene,and DMSO.The structure of the monomer and the polymer was confirmed by elemental analysis,NMR,MS and GPC.The optical and electronic properties of the polymer were investigated by UV-Vis absorption spectroscopy and photoluminescence spectroscopy.The results show that the polymer films emit greenish-blue light (λ max =390 nm) upon UV excitation.Thermo-analysis showed that the glass-transition temperature of the polymer is at 117℃.Moreover,its weight loss was less than 5% on heating to about 349℃ under nitrogen atmosphere.展开更多
Mesogen-Jacketed liquid crystalline polymers were synthesized in various chiral conditions using 1) (\|)\|menthol as a reaction solvent (additive),2) (\|)\|dimenthyl peroxydicarbonate as a chiral free radical initiato...Mesogen-Jacketed liquid crystalline polymers were synthesized in various chiral conditions using 1) (\|)\|menthol as a reaction solvent (additive),2) (\|)\|dimenthyl peroxydicarbonate as a chiral free radical initiator,3) menthyl methacrylate as a comonomer for copolymerization,4) (-)-sparteine-fluorenyllithium as a chiral anionic initiator and 5) a chiral monomer.In the polymerization using a chiral initiator or a chiral solvent,the helix-sense-selection was not found.In the case of the copolymerization,the chiral monomeric unit incorporated into the polymer chain was found to induce liquid crystallinity.Chiral mesogen-Jacketed polymer was also synthesized from chiral monomer 5.However,this polymer did not form a liquid crystal phase although it met the model of Mesogen-Jacketed liquid crystalline polymers.展开更多
基金This project was supported by the Foundation of Peking University for Young Scientist and the National Natural Science Foundation of China.
文摘The synthesis of rod-coil diblock copolymers was achieved for the first time by TEMPO-mediated 'living' free radical polymerization of styrene and 2,5-bis [(4-methoxyphenyl)oxycarbonyl] styrene(MPCS). The block architecture of the two diblock copolymers thus prepared, MPCS-b-St(5400/2400) and MPCS-b-St(10800/8700), was confirmed by GPC, DSC studies and the formation of multimolecular micelles. (Author abstract) 10 Refs.
基金This work was supported by the Foundation of Peking University for Young Scientist and the National Natural Science Foundation of China(Grant No.29874003).
文摘The first TEMPO-mediated 'living' free radical polymerization of liquid crystalline monomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS), was carried out at 130 degrees C with BPO as an initiator. The molecular weight of the polymer can be varied from rather low values to high values while maintaining narrow polydispersity. It was observed that the polymerization of MPCS proceeded much faster than that of styrene. A tentative explanation for this fast polymerization was suggested.
基金This work is supported by the National Natural Science Foundation of China.
文摘Poly{2, 5-bis[(p-methoxyphenyl)oxycarbonyl]styrene} was successfully synthesized. This new polymer has a structure characteristic of mesogen-jacketed liquid cyrstalline polymers (MJLCPs) and does form a liquid crystal phase above its glass transition. It thus became the starting member of a new series of MJLCPs. The synthesis of the polymer as well as the liquid crystalline properties of the polymer and its monomer was discussed. A brief comparison of the new monomer and polymer with some previously reported counterparts was also included.
文摘Mesogen-jacketed liquid crystalline polymer （MJLCP） has attracted great attention because of its rigid conformation, facile synthesis, and structural controllability. In this feature article, the self-assembly of MJLCP-based block copolymers （BCPs） is briefly reviewed, especially the nanostructures of rod-coil diblock copolymers （diBCPs）, rod-rod diBCPs, and triblock copolymers. In addition, the properties of the self-assembled BCPs are also summarized, including their applications as liquid crystalline thermoplastic elastomers and solid polymer electrolytes. The article also discusses the major challenges and future directions in the study of MJLCP-based BCPs.
基金financially supported by the National Natural Science Foundation of China(51343008)
文摘The effects of mesogen-jacketed liquid crystalline polymer poly(dipropyl vinylterephthalate)(PDPVT) on the mechanical and thermal properties of diglycidyl ether of bisphenol-A(DGEBA) epoxy resin were investigated by impact test, tensile test and thermogravimetric analysis(TGA). The mechanism underlying the enhancement of mechanical properties of epoxy resin was studied using 1D wide-angle X-ray diffraction(WAXD) and scanning electron microscope(SEM). It was found that the mechanical properties of 1 wt%–5 wt% PDPVT/DGEBA composites were significantly improved compared to neat epoxy resin. Especially, the epoxy resin with 3 wt% PDPVT had the greatest increase in mechanical properties, with the impact strength, tensile strength and elongation while breaking increased by 87%, 59% and 174%, respectively. The increased mechanical strength was due to the fact that PDPVT maintained liquid crystalline phase in cured PDPVT/DGEBA composites, which would blunt the crack tip and prevent crack propagation. Moreover, PDPVT had slight effect on the thermal stability properties of epoxy resin.
基金This Project was supported by China Postdoctoral Science Foundation and National Natural Science Foundation of China (No. 59873001).
文摘Some new mesogen-jacketed liquid crystalline polymers (MJLCP) with polymer backbones, spacers, and mesogenic units of different structures were synthesized by radical polymerization. The mesomorphic behavior of these polymers was examined using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Their liquid crystallinity is influenced by the variation of polymer backbone, spacer, mesogenic unit and its terminal groups. The results show that 1) a more flexible polymer main-chain is more favorable to the formation of a liquid crystal phase, while 2) a flexible spacer will decrease the 'Jacket Effect' and the liquid crystallinity and 3) a subtle modification of the terminal groups on the mesogenic unit may also have a significant influence on properties of the polymers.
基金This project was supported by China Postdoctoral Science Foundation and National Natural Science Foundation of China (No. 59873001).
文摘New liquid crystalline monomer, 2,5-bis[(4'-methoxyphenoxy)carbonyl]phenyl acrylate was successfully synthesized. Polyacrylate with laterally attached mesogens via ei;ter linkage was also derived. This polymer forms an enantiotropic liquid crystal phase while its monomer exhibits a metastable nematic phase with respect to the crystalline state. However, its liquid crystallinity is very low as compared to that of poly{2,5-bis[(4'-methoxyphenoxy)carbonyl]-styrene}.
基金This work was supported by the National Natural Science Foundation of China(Grant No.20134010)the Ministry of Education of China(Key Project No.104005).
文摘A series of poly{2,5-bis[(4-butoxyphenyl)-oxycarbonyl]styrenes}(PBPCS)with low mo-lecular weight distribution was synthesized by atom transfer radical polymerization(ATRP).The me-somorphic properties were investigated by differential scanning calorimetry(DSC),polarizing optical microscopy(POM)and rheometer.PBPCS showed the phase transition from isotropic into liquid crystal(LC)phase,and the LC phase formed at high temperature and disappeared in the subsequent cooling procedure.Using the WAXD fiber pattern,the phase structure of the PBPCS at higher tem-perature showed hexagonal columnar nematic phase.Experimental results demonstrated that the driving force of the entropy is an important factor during the unusual LC phase formation of PBPCS.
文摘A mesogen-jacketed liquid crystal polymer,poly{2,5 -bis［(4′-hexyloxyphenyl)oxycarbonyl］styrene}(PHPCS),with number-average d molecular weight of 1.28×１０5 and polydispersity of 1.48 was prepared vi a 2,2,6,6 -tetramethyl-piperidinyloxy mediated free radical polymerization.The thermotr opic behavior was studied by a combination of differential scanning calorimetry, thermogravimetry,polarized optical microscope and wide-angle X-ray diffracti on.PHPCS was not crystalline over the entire temperature region studied.On hea ting,PHPCS first became an isotropic melt at glass transition temperature (T g) and then a mesophase at temperatures much higher than T g.On subseq uent cooling,the formed ordered phase disappeared above T g.Contrary to t heoretical predictions and previous experimental observations,the transition fr om isotropic melt to liquid crystalline phase was an endothermic process and th e order-disorder transition took place with concurrence of heat release.
文摘A series of monomers {2,5-bis[(5-alkyl-phenyl)-1,3,4-oxadiazole] styrene}(BOXE) were designed and synthesized.By radical polymerization initiated BPO with a novel series of mesogen-jacketed polymers containing 1,3,4-oxadiazole were prepared.Molecular weight and molecular weight distribution of polymers were measured by GPC.The glass transition temperature (T_g) and thermal stability of polymers were studied by DSC and TGA.The results indicate that these polymers have good thermal stability.These liquid crystal polymers have well defined structure,and possess special photo-electronic properties.
文摘It is reported report herein the synthesis and characterization of a new mesogen-jacketed polymer containing an electron deficient oxadiazole unit __ poly{2,5-bis[(5-tert-butylphenyl)-1,3,4-oxadiazole]styrene} (BBPOS).BBPOS can be dissolved in THE,CHCl-3,xylene,and DMSO.The structure of the monomer and the polymer was confirmed by elemental analysis,NMR,MS and GPC.The optical and electronic properties of the polymer were investigated by UV-Vis absorption spectroscopy and photoluminescence spectroscopy.The results show that the polymer films emit greenish-blue light (λ max =390 nm) upon UV excitation.Thermo-analysis showed that the glass-transition temperature of the polymer is at 117℃.Moreover,its weight loss was less than 5% on heating to about 349℃ under nitrogen atmosphere.
文摘Mesogen-Jacketed liquid crystalline polymers were synthesized in various chiral conditions using 1) (\|)\|menthol as a reaction solvent (additive),2) (\|)\|dimenthyl peroxydicarbonate as a chiral free radical initiator,3) menthyl methacrylate as a comonomer for copolymerization,4) (-)-sparteine-fluorenyllithium as a chiral anionic initiator and 5) a chiral monomer.In the polymerization using a chiral initiator or a chiral solvent,the helix-sense-selection was not found.In the case of the copolymerization,the chiral monomeric unit incorporated into the polymer chain was found to induce liquid crystallinity.Chiral mesogen-Jacketed polymer was also synthesized from chiral monomer 5.However,this polymer did not form a liquid crystal phase although it met the model of Mesogen-Jacketed liquid crystalline polymers.
