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
H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene ox...H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide） （PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.展开更多
The effect of flexible spacer length on the liquid crystalline property of ABA-type triblock copolymers containing azobenzene groups was investigated. For the study, the monomers, n-[4-(4-ethoxyphenylazo)phenoxy]alkyl...The effect of flexible spacer length on the liquid crystalline property of ABA-type triblock copolymers containing azobenzene groups was investigated. For the study, the monomers, n-[4-(4-ethoxyphenylazo)phenoxy]alkyl methacrylates with varying methylene groups (n = 0, 2, 6) were used to synthesize a series of azobenzene-containing amphiphilic triblock copolymers PAnC–PEG–PAnC by atom transfer radical polymerization (ATRP). Differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and one-dimensional X-ray diffraction (1D WAXD) have shown that the glass transition temperatures of these copolymers decreased with increasing n, PA0C–PEG–PA0C has no mesophase, while both PA2C–PEG–PA2C and PA6C–PEG–PA6C have a nematic mesophase. These differences derive from the length of spacer groups between the polymer backbone and side-chain LC monomers.展开更多
A wholly-aromatic thermotropic liquid crystalline polymer (WATLCP) composed of p-hydroxybenzoic acid (HBA), 4,4'-dihydroxy bisphenyl (BP), terephthalic acid (TPA), m-phthalic acid (MPA) was synthesized. It was sym...A wholly-aromatic thermotropic liquid crystalline polymer (WATLCP) composed of p-hydroxybenzoic acid (HBA), 4,4'-dihydroxy bisphenyl (BP), terephthalic acid (TPA), m-phthalic acid (MPA) was synthesized. It was symbolized by BP-LCP. Using a similar method, a new copolymer BP-PSF was prepared. BP-PSF has a semi-flexible chain polysulfone and a rigid-rod chain like BP-LCP. By FT-IR, polarizing microscope and DSC technique, the structures and properties of BP-LCP and BP-PSF were studied.展开更多
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
A new side chain liquid crystalline poly[4 (methacryloxy)hexanoloxy 4′ benzyloxy biphenyl] was synthesized. The phase behavior of the monomer and homopolymer was studied. The monomer shows a smectic B phase, while...A new side chain liquid crystalline poly[4 (methacryloxy)hexanoloxy 4′ benzyloxy biphenyl] was synthesized. The phase behavior of the monomer and homopolymer was studied. The monomer shows a smectic B phase, while the homopolymer shows a nematic phase. The nonmesogenic nonlinear optical group was introduced to synthesize a series of side chain liquid crystalline copolymers which also show a nematic phase. Owing to the liquid crystallinity of the copolymer has been the orientational stability improved, down the relax of the orientation slowed and the nonlinear optical properties enhanced.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
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
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
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
Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility wit...Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.展开更多
A liquid crystalline block copolymer (BCPE) was synthesized from bis phenol A epoxy oligomer and liquid crystalline polyester (PBHT) which was prepared from polyhexamethylene bis (4 oxybenzoates) and terephthaloyl dic...A liquid crystalline block copolymer (BCPE) was synthesized from bis phenol A epoxy oligomer and liquid crystalline polyester (PBHT) which was prepared from polyhexamethylene bis (4 oxybenzoates) and terephthaloyl dichloride by solution polymerization.The intrinsic viscosity ( η inh ) of the polymers was determined using an ubbelohde viscometer in phenyl hydroxide/1,1,2,2 tetrachloroethane mix solvent (1:1) at 30℃, and the results showed that the η inh values of PBHT and BCPE are 0.16 dL/g and 0.46 dL/g respectively. FTIR analysis identified the reaction between bis phenol A epoxy oligomer and PBHT. The crystalline properties of polymers were investigated with DSC and WAXD, and the results found that the crystallinity of BCPE is inferior to that of PBHT due to addition of amorphous epoxy. Thermotropic liquid crystalline nematic phase textures of polymers were observed under a polarizing microscope with hot stage.展开更多
The effect of a new liquid crystalline copolymer(LCP-H2) on the crystallization structure of isotactic polypropylene(iPP) was investigated using wide-angle X-ray diffraction.The experimental results show that LCP-H2 o...The effect of a new liquid crystalline copolymer(LCP-H2) on the crystallization structure of isotactic polypropylene(iPP) was investigated using wide-angle X-ray diffraction.The experimental results show that LCP-H2 of low mass fraction can induce β-form in iPP.The nucleating activity of LCP-H2 mainly depended on its content and crystallization temperature.The content of β-form(Kβ) increased with increasing the nucleator content and crystallization temperature,Kβ value reached a maximum value(35%) when the nucleator mass fraction was 0.8% and the crystallization temperature was 125 ℃.展开更多
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financial support from the National Natural Science Foundation of China(No.20134020)the Science Research Fund of the Chinese Ministry of Education(No.104005)the Science Research Fund of Shandong Provincial Education Department of China(No.105D11).
文摘H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide） （PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.
文摘The effect of flexible spacer length on the liquid crystalline property of ABA-type triblock copolymers containing azobenzene groups was investigated. For the study, the monomers, n-[4-(4-ethoxyphenylazo)phenoxy]alkyl methacrylates with varying methylene groups (n = 0, 2, 6) were used to synthesize a series of azobenzene-containing amphiphilic triblock copolymers PAnC–PEG–PAnC by atom transfer radical polymerization (ATRP). Differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and one-dimensional X-ray diffraction (1D WAXD) have shown that the glass transition temperatures of these copolymers decreased with increasing n, PA0C–PEG–PA0C has no mesophase, while both PA2C–PEG–PA2C and PA6C–PEG–PA6C have a nematic mesophase. These differences derive from the length of spacer groups between the polymer backbone and side-chain LC monomers.
文摘A wholly-aromatic thermotropic liquid crystalline polymer (WATLCP) composed of p-hydroxybenzoic acid (HBA), 4,4'-dihydroxy bisphenyl (BP), terephthalic acid (TPA), m-phthalic acid (MPA) was synthesized. It was symbolized by BP-LCP. Using a similar method, a new copolymer BP-PSF was prepared. BP-PSF has a semi-flexible chain polysulfone and a rigid-rod chain like BP-LCP. By FT-IR, polarizing microscope and DSC technique, the structures and properties of BP-LCP and BP-PSF were studied.
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A new side chain liquid crystalline poly[4 (methacryloxy)hexanoloxy 4′ benzyloxy biphenyl] was synthesized. The phase behavior of the monomer and homopolymer was studied. The monomer shows a smectic B phase, while the homopolymer shows a nematic phase. The nonmesogenic nonlinear optical group was introduced to synthesize a series of side chain liquid crystalline copolymers which also show a nematic phase. Owing to the liquid crystallinity of the copolymer has been the orientational stability improved, down the relax of the orientation slowed and the nonlinear optical properties enhanced.
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(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.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supported by the National Natural Science Foundation of China(52003293,51927806,52272258)the Fundamental Research Funds for the Central Universities(2023ZKPYJD07)the Beijing Nova Program(20220484214).
文摘Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.
文摘A liquid crystalline block copolymer (BCPE) was synthesized from bis phenol A epoxy oligomer and liquid crystalline polyester (PBHT) which was prepared from polyhexamethylene bis (4 oxybenzoates) and terephthaloyl dichloride by solution polymerization.The intrinsic viscosity ( η inh ) of the polymers was determined using an ubbelohde viscometer in phenyl hydroxide/1,1,2,2 tetrachloroethane mix solvent (1:1) at 30℃, and the results showed that the η inh values of PBHT and BCPE are 0.16 dL/g and 0.46 dL/g respectively. FTIR analysis identified the reaction between bis phenol A epoxy oligomer and PBHT. The crystalline properties of polymers were investigated with DSC and WAXD, and the results found that the crystallinity of BCPE is inferior to that of PBHT due to addition of amorphous epoxy. Thermotropic liquid crystalline nematic phase textures of polymers were observed under a polarizing microscope with hot stage.
文摘The effect of a new liquid crystalline copolymer(LCP-H2) on the crystallization structure of isotactic polypropylene(iPP) was investigated using wide-angle X-ray diffraction.The experimental results show that LCP-H2 of low mass fraction can induce β-form in iPP.The nucleating activity of LCP-H2 mainly depended on its content and crystallization temperature.The content of β-form(Kβ) increased with increasing the nucleator content and crystallization temperature,Kβ value reached a maximum value(35%) when the nucleator mass fraction was 0.8% and the crystallization temperature was 125 ℃.
