The properties and structures of thermotropical liquid crystalline copolyesters based on p-hydroxybenzoic acid (PHBA), terephthalic acid (TPR) and bisphenol A (BPA) were studied by DSC, WAXD, hot stage polarized micro...The properties and structures of thermotropical liquid crystalline copolyesters based on p-hydroxybenzoic acid (PHBA), terephthalic acid (TPR) and bisphenol A (BPA) were studied by DSC, WAXD, hot stage polarized microscopy and NMR. It was found that most of the copolyesters were soluble in many common organic solvents. The copolyesters had low T-m/T-f values and a broad range of liquid crystal phase, making the polymers readily melt-processable. The effects of annealing at different temperatures on the copolyester containing 33% PHBA were also discussed. It was noted that annealing at ca. 200 degrees C (below Tc - n) could lead to the increasing of the crystallinity of the copolyester while the microstructure and sequence structure had not changed. Annealing at ca. 280 degrees C (near Tc - n) could bring a change of crystal and sequence structure and simultaneously made the microdomains be ordered more perfectly.展开更多
A novel series of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 was prepared via solution conde...A novel series of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4＇-（a;arhexanedioyloxy） dibenzoyl dichloride （MI）, 2,5-bis（p-octyloxybenzoyloxy） hydro-quinone （M2） and cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 （M3）. Monomer MI was synthesized by esterification and substitution of adipoyl chloride with p-hydroxybenzoic acid, monomer M2 was synthesized by esterfication and reduction reaction of 2,5-dihydroxybenzoquinone and p-octanoxybenzoyl chloride and monomer M3 was synthesized by diazotization and coupling reaction of cis-diaminodibenzo-18-crown-6 with phenol. The molecular weights of copolyesters are not high, and the intrinsic viscosity [η] of copolyesters ranges from 0.25-0.35. The monomers＇ structures were identified by using elemental analysis, IR, UV, ^1H-NMR, MS, etc. All the copolyesters are yellowish powders and insoluble in THF and CHC13 at room temperature except cPg. The properties of copolyesters were investigated by using GPC, [η] , DSC, TG, WAXD and POM. It was found that all the copolyesters entered into liquid crystal phase when they were heated to above their melting temperature （Tin）. The typical smectic and nematic phase texture can be observed on POM. Their mesophase transition temperature and thermal stability change regularly with varying the content of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 unit in the copolyesters.展开更多
Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild con...Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild conditions. The electron-rich hydroxyl groups of bisphenols favoured the polycondensation reaction and the order of relative reactivities of bisphenols is as follow:bisphenoI-A> hydroquinone ～ bisphenol-S> chlorohydroquinone. The mesomorphic properties of copolyesters were examined by birefringence under polarizing microscope, melt transparency. DSC and X-ray diffraction. The minimum molar fraction of mesogenic units needed for the appearance of liquid crystallinity is not higher than 0. 1 despite of the different varieties and lengths of the spacers studied.展开更多
A novel series of liquid crystalline copolyesters with T-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4′-bis(4-hydroxyphenylazo)dibenzo-18-crown-6 was prepared via solution condensation polyme...A novel series of liquid crystalline copolyesters with T-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4′-bis(4-hydroxyphenylazo)dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4′-(α,ω-hexanedioyloxy)dibenzoyl dichloride(M_1),2-(4′-ethoxyphenyl)hydroquinone(M_2)and cis-4,4′-bis(4- hydroxyphenylazo)dibenzo-18-crown-6(M_3).The molecular weights of copolyesters are not high,and the intrinsic viscosity [η]of copolyesters ranges from 0.29-0.43.The monomers ...展开更多
In this paper, the sequence structure of TPA/EG/PHB liquid crystalline copolyesters made from different synthetic methods has been studied by;H-NMR with the help of computer program of processing peaks. The results sh...In this paper, the sequence structure of TPA/EG/PHB liquid crystalline copolyesters made from different synthetic methods has been studied by;H-NMR with the help of computer program of processing peaks. The results showed that the ether bonds were not observed in TPA./EG/PHB copolyesters and the synthetic process had a great effect on their sequence structure. Under certain conditions, the high,random TPA/EG/PHB copolyesters which were considered to have higher performances than PET/xPHB could be obtained.展开更多
文摘The properties and structures of thermotropical liquid crystalline copolyesters based on p-hydroxybenzoic acid (PHBA), terephthalic acid (TPR) and bisphenol A (BPA) were studied by DSC, WAXD, hot stage polarized microscopy and NMR. It was found that most of the copolyesters were soluble in many common organic solvents. The copolyesters had low T-m/T-f values and a broad range of liquid crystal phase, making the polymers readily melt-processable. The effects of annealing at different temperatures on the copolyester containing 33% PHBA were also discussed. It was noted that annealing at ca. 200 degrees C (below Tc - n) could lead to the increasing of the crystallinity of the copolyester while the microstructure and sequence structure had not changed. Annealing at ca. 280 degrees C (near Tc - n) could bring a change of crystal and sequence structure and simultaneously made the microdomains be ordered more perfectly.
基金This work was supported by the National Natural Science Foundation of China(No.29974026)the Natural Science Foundation of Henan Province.
文摘A novel series of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4＇-（a;arhexanedioyloxy） dibenzoyl dichloride （MI）, 2,5-bis（p-octyloxybenzoyloxy） hydro-quinone （M2） and cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 （M3）. Monomer MI was synthesized by esterification and substitution of adipoyl chloride with p-hydroxybenzoic acid, monomer M2 was synthesized by esterfication and reduction reaction of 2,5-dihydroxybenzoquinone and p-octanoxybenzoyl chloride and monomer M3 was synthesized by diazotization and coupling reaction of cis-diaminodibenzo-18-crown-6 with phenol. The molecular weights of copolyesters are not high, and the intrinsic viscosity [η] of copolyesters ranges from 0.25-0.35. The monomers＇ structures were identified by using elemental analysis, IR, UV, ^1H-NMR, MS, etc. All the copolyesters are yellowish powders and insoluble in THF and CHC13 at room temperature except cPg. The properties of copolyesters were investigated by using GPC, [η] , DSC, TG, WAXD and POM. It was found that all the copolyesters entered into liquid crystal phase when they were heated to above their melting temperature （Tin）. The typical smectic and nematic phase texture can be observed on POM. Their mesophase transition temperature and thermal stability change regularly with varying the content of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 unit in the copolyesters.
文摘Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild conditions. The electron-rich hydroxyl groups of bisphenols favoured the polycondensation reaction and the order of relative reactivities of bisphenols is as follow:bisphenoI-A> hydroquinone ～ bisphenol-S> chlorohydroquinone. The mesomorphic properties of copolyesters were examined by birefringence under polarizing microscope, melt transparency. DSC and X-ray diffraction. The minimum molar fraction of mesogenic units needed for the appearance of liquid crystallinity is not higher than 0. 1 despite of the different varieties and lengths of the spacers studied.
基金This work was supported by the National Natural Science Foundation of China(No.29974026)the Natural Science Foundation of Henan Province(No.0211021100)the Education Department Foundation of Henan Province(No.20021500004).
文摘A novel series of liquid crystalline copolyesters with T-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4′-bis(4-hydroxyphenylazo)dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4′-(α,ω-hexanedioyloxy)dibenzoyl dichloride(M_1),2-(4′-ethoxyphenyl)hydroquinone(M_2)and cis-4,4′-bis(4- hydroxyphenylazo)dibenzo-18-crown-6(M_3).The molecular weights of copolyesters are not high,and the intrinsic viscosity [η]of copolyesters ranges from 0.29-0.43.The monomers ...
文摘In this paper, the sequence structure of TPA/EG/PHB liquid crystalline copolyesters made from different synthetic methods has been studied by;H-NMR with the help of computer program of processing peaks. The results showed that the ether bonds were not observed in TPA./EG/PHB copolyesters and the synthetic process had a great effect on their sequence structure. Under certain conditions, the high,random TPA/EG/PHB copolyesters which were considered to have higher performances than PET/xPHB could be obtained.
