Multi-scales relaxation processes of short fiber of a nematic liquid crystalline copolymer(LCP)in polycarbonate matrix were investigated.First,the structure relaxation of LCP was studied by rheology.The relaxation spe...Multi-scales relaxation processes of short fiber of a nematic liquid crystalline copolymer(LCP)in polycarbonate matrix were investigated.First,the structure relaxation of LCP was studied by rheology.The relaxation spectrum of the nematic liquid crystalline copolymer at 295℃was calculated from the combined dynamic modulus.There are three kinds of relaxation mechanisms for nematic liquid crystalline copotymer:the relaxation of chain orientation,the relaxation of deformed polydomains and the coalescence of pol...展开更多
The synthesis and phase behaviour of chiral combined main/side chain liquid crystallinecopolymers containing pendant group constituted by chiral side group and trans-azobenzenemoiety with nitro end group are described...The synthesis and phase behaviour of chiral combined main/side chain liquid crystallinecopolymers containing pendant group constituted by chiral side group and trans-azobenzenemoiety with nitro end group are described. The formation of liquid crystalline polymorphism ofcopolymers is influenced by various contents of achiral side group.展开更多
A series of liquid crystalline multi-block copolymers poly[1.6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segment lengths were synthesized in tetrachloroethane ...A series of liquid crystalline multi-block copolymers poly[1.6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segment lengths were synthesized in tetrachloroethane by solution polycondensation in which hydroxyl terminated PC and acyl chloride terminated PHTH-6 were used. It is found that block copolymers with high molecular weight and well-defined structures were obtained. All the block copolymers exhibit a nematic liquid crystalline texture.展开更多
Liquid crystalline multi-block copolymers poly[1,6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segments of polycarbonate (PC) and thermotropic polyester PHTH-6 w...Liquid crystalline multi-block copolymers poly[1,6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segments of polycarbonate (PC) and thermotropic polyester PHTH-6 were synthesized in tetrachloroethane at 144 similar to 146 degrees C. The influence of segment length on the resulting phase structure and thermal behavior of block copolymers was also discussed. It is demonstrated by TEM and DMA that the resulting block copolymers show a considerable microphase separation. The degree of phase separation and the thermal behavior of the block copolymers are strongly dependent on the molecular weight of the segments incorporated.展开更多
A series of novel side-chain liquid crystalline(SCLC)copolymers were synthesized by attaching two distinct mesogenic units,namely a chiral cholesteryl-based monomer(M1)and an achiral biphenyl-based monomer(M2),to a po...A series of novel side-chain liquid crystalline(SCLC)copolymers were synthesized by attaching two distinct mesogenic units,namely a chiral cholesteryl-based monomer(M1)and an achiral biphenyl-based monomer(M2),to a poly(3-mercaptopropylmethylsiloxane)(PMMS)backbone via thiol-ene click chemistry.The influence of side chain composition on the self-assembly behavior and phase structures of these SCLC copolymers was systematically investigated using different instrument.Results indicate that three distinct liquid crystalline phases and four unique molecular configurations were identified within the polymer series,with the emergence of the liquid crystalline phase being a synergistic outcome of the two distinct side chains.This study underscores the critical influence of side chain dimensions,rigidity,and spatial volume on the self-assembly structures and phase characteristics of liquid crystalline polymers,providing valuable insights for the rational design and development of advanced functional materials with tailored properties.展开更多
Heavy metallic salts are capable to bind with proteins and cause detrimental fibrilization in living cells.Herein,we report a similar case of supramolecular polymerization and thus fibrilization from a liquid crystall...Heavy metallic salts are capable to bind with proteins and cause detrimental fibrilization in living cells.Herein,we report a similar case of supramolecular polymerization and thus fibrilization from a liquid crystalline(LC)block copolymer(BCP)initiated by heavy metallic salts.Analogous to the naturally-occurring process,LC BCP“monomers”could bind with metallic salts to form small aggregates,which functioned as seeds to trigger the subsequent supramolecular polymerization of the rest BCP monomers,to produce highly uniform supramolecular polymers.The lengths of the resultant supramolecular polymer fibrils were linearly proportional to the ratios between the BCP and the metallic salts,and largely influenced by the choice of metallic cations,as well as the counterions.Lastly,this method was used to polymerize two different diblock copolymer“monomers”to produce pentablock supramolecular polymers in a one-pot manner.展开更多
We designed and synthesized a triarm star-shaped rod-rod block copolymer(BCP),(poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene}-block-poly(γ-benzyl-L-glutamate))3,(PMPCS-b-PBLG)3. The triarm core with th...We designed and synthesized a triarm star-shaped rod-rod block copolymer(BCP),(poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene}-block-poly(γ-benzyl-L-glutamate))3,(PMPCS-b-PBLG)3. The triarm core with three PMPCS-N3 segments was prepared by copper-mediated atom transfer radical polymerization of 2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene initiated by a trifunctional initiator and a subsequent azide reaction. And the PBLG block with alkyne functionality was synthesized through ring-opening polymerization of γ-benzyl-L-glutamate N-carboxyanhydride initiated by propargylamine. Finally, Huisgen's 1,3-dipolar cycloaddition was employed to combine the triarm(PMPCS-N3)3 and PBLG segments. The chemical structure of the BCP was confirmed by 1H-NMR spectroscopy, Fourier-transform infrared spectroscopy, and gel permeation chromatographic analysis. Results from differential scanning calorimetry, polarized light microscopy, one-dimensional and two-dimensional wide-angle X-ray diffraction, and transmission electron microscopy techniques demonstrate that the triarm star-shaped rod-rod BCP self-assembles into a hexagon-in-lamella morphology, with the PMPCS block in the columnar nematic phase and the PBLG block in the hexagonal columnar arrangement packed in bilayers due to the rigid nature of the two blocks and the covalent connections in the star-shaped BCP.展开更多
基金This work was financially supported by the National Natural Science Foundation of China(Nos. 20174024,20204007 and 50290090).
文摘Multi-scales relaxation processes of short fiber of a nematic liquid crystalline copolymer(LCP)in polycarbonate matrix were investigated.First,the structure relaxation of LCP was studied by rheology.The relaxation spectrum of the nematic liquid crystalline copolymer at 295℃was calculated from the combined dynamic modulus.There are three kinds of relaxation mechanisms for nematic liquid crystalline copotymer:the relaxation of chain orientation,the relaxation of deformed polydomains and the coalescence of pol...
文摘The synthesis and phase behaviour of chiral combined main/side chain liquid crystallinecopolymers containing pendant group constituted by chiral side group and trans-azobenzenemoiety with nitro end group are described. The formation of liquid crystalline polymorphism ofcopolymers is influenced by various contents of achiral side group.
文摘A series of liquid crystalline multi-block copolymers poly[1.6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segment lengths were synthesized in tetrachloroethane by solution polycondensation in which hydroxyl terminated PC and acyl chloride terminated PHTH-6 were used. It is found that block copolymers with high molecular weight and well-defined structures were obtained. All the block copolymers exhibit a nematic liquid crystalline texture.
文摘Liquid crystalline multi-block copolymers poly[1,6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segments of polycarbonate (PC) and thermotropic polyester PHTH-6 were synthesized in tetrachloroethane at 144 similar to 146 degrees C. The influence of segment length on the resulting phase structure and thermal behavior of block copolymers was also discussed. It is demonstrated by TEM and DMA that the resulting block copolymers show a considerable microphase separation. The degree of phase separation and the thermal behavior of the block copolymers are strongly dependent on the molecular weight of the segments incorporated.
基金financially supported by the National Natural Science Foundation of China(Nos.52263033 and 52202081)China Postdoctoral Science Foundation Funded Project(No.2021M690954)+3 种基金Natural Science Foundation of Gansu Province(No.20JR10RA105)the Natural Science Foundation of Hunan Province(No.2022JJ30152)the graduate research funding project of Northwest Normal University(No.2023KYZZ-S157)Natural Science Foundation of Jiangxi Province,China(No.20232BAB204030)。
文摘A series of novel side-chain liquid crystalline(SCLC)copolymers were synthesized by attaching two distinct mesogenic units,namely a chiral cholesteryl-based monomer(M1)and an achiral biphenyl-based monomer(M2),to a poly(3-mercaptopropylmethylsiloxane)(PMMS)backbone via thiol-ene click chemistry.The influence of side chain composition on the self-assembly behavior and phase structures of these SCLC copolymers was systematically investigated using different instrument.Results indicate that three distinct liquid crystalline phases and four unique molecular configurations were identified within the polymer series,with the emergence of the liquid crystalline phase being a synergistic outcome of the two distinct side chains.This study underscores the critical influence of side chain dimensions,rigidity,and spatial volume on the self-assembly structures and phase characteristics of liquid crystalline polymers,providing valuable insights for the rational design and development of advanced functional materials with tailored properties.
基金financially supported by the National Natural Science Foundation of China(Nos.51973019 and 22175024).
文摘Heavy metallic salts are capable to bind with proteins and cause detrimental fibrilization in living cells.Herein,we report a similar case of supramolecular polymerization and thus fibrilization from a liquid crystalline(LC)block copolymer(BCP)initiated by heavy metallic salts.Analogous to the naturally-occurring process,LC BCP“monomers”could bind with metallic salts to form small aggregates,which functioned as seeds to trigger the subsequent supramolecular polymerization of the rest BCP monomers,to produce highly uniform supramolecular polymers.The lengths of the resultant supramolecular polymer fibrils were linearly proportional to the ratios between the BCP and the metallic salts,and largely influenced by the choice of metallic cations,as well as the counterions.Lastly,this method was used to polymerize two different diblock copolymer“monomers”to produce pentablock supramolecular polymers in a one-pot manner.
基金financially supported by the National Natural Science Foundation of China(Nos.20990232 and 21174006)
文摘We designed and synthesized a triarm star-shaped rod-rod block copolymer(BCP),(poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene}-block-poly(γ-benzyl-L-glutamate))3,(PMPCS-b-PBLG)3. The triarm core with three PMPCS-N3 segments was prepared by copper-mediated atom transfer radical polymerization of 2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene initiated by a trifunctional initiator and a subsequent azide reaction. And the PBLG block with alkyne functionality was synthesized through ring-opening polymerization of γ-benzyl-L-glutamate N-carboxyanhydride initiated by propargylamine. Finally, Huisgen's 1,3-dipolar cycloaddition was employed to combine the triarm(PMPCS-N3)3 and PBLG segments. The chemical structure of the BCP was confirmed by 1H-NMR spectroscopy, Fourier-transform infrared spectroscopy, and gel permeation chromatographic analysis. Results from differential scanning calorimetry, polarized light microscopy, one-dimensional and two-dimensional wide-angle X-ray diffraction, and transmission electron microscopy techniques demonstrate that the triarm star-shaped rod-rod BCP self-assembles into a hexagon-in-lamella morphology, with the PMPCS block in the columnar nematic phase and the PBLG block in the hexagonal columnar arrangement packed in bilayers due to the rigid nature of the two blocks and the covalent connections in the star-shaped BCP.