It was found that traces of water in the reaction medium would result in a great increase of gel and a decrease of Molecular weight of the poly(2-methoxy,5-(2'-ethylhexyloxy)-1,4-phenylene vinylene) during the pol...It was found that traces of water in the reaction medium would result in a great increase of gel and a decrease of Molecular weight of the poly(2-methoxy,5-(2'-ethylhexyloxy)-1,4-phenylene vinylene) during the polymerization, which ultimately led to inferior film qualities and device properties. The device (ITO/PEDOT/MEH-PPV/Ba/Al) with MEH-PPV prepared under dry conditions has an external quantum efficiency of above 2.0%.展开更多
A novel hyperbranched poly(phenylene oxide) (HPPO) with phenolic terminal groups was prepared from 4-bromo-4',4"-dihydroxytriphenylmethane as AB2 monomer in dimethylsulfoxide (DMSO) via a modified Ullmann reac...A novel hyperbranched poly(phenylene oxide) (HPPO) with phenolic terminal groups was prepared from 4-bromo-4',4"-dihydroxytriphenylmethane as AB2 monomer in dimethylsulfoxide (DMSO) via a modified Ullmann reaction. The molecular weight and polydispersity (PD) of the resulting polymers increased with increasing reaction time. In the presence of core molecules (bisphenol A and 1,3,5-trihydroxybenzene), which have the similar molecular backbones to the reactive monomer, the molecular weight could be controlled by varying the core-to-monomer ratio. Incorporation of a very small amount of core molecules could lead to a higher molecular weight as compared with that without the addition of core molecules. However, when the core content reached certain extent, the molecular weight would decrease with the further increase in the core content. A new similar behavior of control over the PD was also obtained. The resulting polymers were characterized by ^1H-NMR, ^13C-NMR, FT-IR, and GPC.展开更多
Poly(phenylene sulfide/ether) (PPSE) was synthesized from 4,4'-dihydroxydiphenyl sulfide and 4,4'-dichlorodiphenyl sulfide in solution by nucleophilic substitution reaction. The resulting polymer was characteriz...Poly(phenylene sulfide/ether) (PPSE) was synthesized from 4,4'-dihydroxydiphenyl sulfide and 4,4'-dichlorodiphenyl sulfide in solution by nucleophilic substitution reaction. The resulting polymer was characterized by viscosity measurement, elemental analysis, FT-IR, ^1H NMR, X-ray diffraction and thermal analysis. The results showed that the viscosities of the resulting polymer were above 0.68 dL/g, and the linear chain structure of product was confirmed. PPSE had the same reflex indices as poly(p-phenylene sulfide), an orthorhombic crystalline with unit cell a=0.853, b=0.562, c=1.026nm. The melting temperature, glass transition temperature and initial decomposition temperature were found to be 228℃, 85℃ and 325℃, respectively. The product was soluble in common organic solvents such as NMP, N, N'-dimethylformamide, N, N'-dimethylacetamide and 1,2-dichloroethane.展开更多
Both aliphatic and aromatic ketones are efficiently transfer-hydrogenated by propan-2-ol under mild conditions in the presence of a catalytic amount of poly(2,6-dimethyl-1,4-Phenylene oxide) (PPO) anchored ruthenium...Both aliphatic and aromatic ketones are efficiently transfer-hydrogenated by propan-2-ol under mild conditions in the presence of a catalytic amount of poly(2,6-dimethyl-1,4-Phenylene oxide) (PPO) anchored ruthenium complex and sodium hydroxide. An important feature of this polymer anchored catalyst is its stability in air.展开更多
In this work, a quantum-chemical investigation on the structural and opto-electronic properties of oligo(thiophene-phenylene) (4TP) is carried out. The results are discussed in comparison with the properties of co...In this work, a quantum-chemical investigation on the structural and opto-electronic properties of oligo(thiophene-phenylene) (4TP) is carried out. The results are discussed in comparison with the properties of corresponding oligothiophene (8T) and oligophenylene (8P). As the opto-electronic properties of this type of conducting polymers are governed by their electronic band gap, we shall also present a comparison among HOMO, LUMO and band gap energies of these three materials.展开更多
In this paper the percolation theory is employed to study the insulator-to-conductortransition in sulphonated poly(phenylene oxide)(SPPO) polymer membranes.The membranes withdifferent sulphonation degree were prep...In this paper the percolation theory is employed to study the insulator-to-conductortransition in sulphonated poly(phenylene oxide)(SPPO) polymer membranes.The membranes withdifferent sulphonation degree were prepared and infrared characterized.The transition thresholdwas calculated by the experimental data of membrane conductivities and the coordination numberwas thus estimated.The functional group-SO<sub>3</sub>H distribution in the membrane was evaluated inaccordance with the calculations and showed a non-random dispersion on the microscopic scale.展开更多
This paper investigates the possibility of attaining sulphonated poly(phenylene oxide) (SPPO) with a relativelyhigher sulfonation degree. To achieve this aim, the approach we adopt is to improve the solubility of the ...This paper investigates the possibility of attaining sulphonated poly(phenylene oxide) (SPPO) with a relativelyhigher sulfonation degree. To achieve this aim, the approach we adopt is to improve the solubility of the final product in themixed solvent so that the sulfonation may take place between the bulk solutions and PPO powders even at higher sulfonationdegree. It is shown that the addition of a proper amount of dimethyl formide (DMF) to the conventional PPO-chloroformsystem can actually enhance the sulfonation effect. The solvent composition is then correlated with the sulfonation degreebased on the solubility parameters. It is interesting to find that solubility parameters between the mixed solvent and theprecipitated products keep an approximately unchanged value at about 4.9, which is just equal to that when pure chloroformis used, though the solubility parameters of both solvents increase with the content of DMF in solution. This may be the mainreason why the addition of DMF can reduce the precipitation and improve the ion exchange capacity (IEC) of SPPOpolymer.展开更多
The apparent solubility (S), concentration-average diffusivity (D), and permeability (P), for C0_2, CH_4 and N_2 through PPO and aryl-brominated PPO at 35℃ for pressure ranging from 1 to 26 atm are reported. It is fo...The apparent solubility (S), concentration-average diffusivity (D), and permeability (P), for C0_2, CH_4 and N_2 through PPO and aryl-brominated PPO at 35℃ for pressure ranging from 1 to 26 atm are reported. It is found that P, D, and S of the membranes to all the three gases vary with the extent of bromination. S increases with the increase of the percent of bromine in each case, but D to CO_2 increases remarkably only at higher degree of brominafion, and therefore, P to CO_2 is increased by more than 100% over a wide range ofpressure in the case. The solubility data are well described by the dual mode sorption model. It is found that the gas molecules sorbed by the Langmuir mode are relatively more immobilized and the contribution of the nonequilibrinm character of the polymer to gas permeation increases obviously for CO_2 and is hardly changed for CH_4 with increasing bromine content. These observations are interpreted in terms of changes in specific free volume (SFV)and the cohesive energy density (CED) of the polymers.展开更多
Poly(phenylene sulfide amide) (PPSA) has been synthesized by using sulfur as S source which reacts with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure. The polymer structures ...Poly(phenylene sulfide amide) (PPSA) has been synthesized by using sulfur as S source which reacts with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure. The polymer structures were determined by elemental analysis, FT-IR and H-1-NMR. It is shown that the yielded polymer has linear structure and its structure unit is -p-C6H4-CONH -p-C6H4-S-. The polymer morphology was studied by X-ray diffraction and polarized microscopy. The results show that PPSA is a crystalline polymer and its spherulites are the aggregation of nontwisting lamella or micro-thread structure. Under shearing force, these crystals are dispersed to form micro-fibrillar structure. The decomposition kinetics of PPSA was also studied at different heating rates. The decomposition energy of PPSA is higher than that of PPS.展开更多
A first-principles computational method based on the hybrid density functional theory is developed to simulate the electronic transport properties of oligomeric phenylene ethynylene molecular junctions with H2O molecu...A first-principles computational method based on the hybrid density functional theory is developed to simulate the electronic transport properties of oligomeric phenylene ethynylene molecular junctions with H2O molecules accumulated in the vicinity as recently reported by Na et al. [Nanotechnology 18 424001 (2007)]. The numerical results show that the hydrogen bonds between the oxygen atoms of the oligomeric phenylene ethynylene molecule and H2O molecules result in the localisation of the molecular orbitals and lead to the lower transition peaks. The H2O molecular chains accumulated in the vicinity of the molecular junction can not only change the electronic structure of the molecular junctions, but also open additional electronic transport pathways. The obvious influence of H2O molecules on the electronic structure of the molecular junction and its electronic transport properties is thus demonstrated.展开更多
A soluble poly(meta-phenylene) derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction. The polymer is soluble in common organic solvents, and the number-average molecular weigh...A soluble poly(meta-phenylene) derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction. The polymer is soluble in common organic solvents, and the number-average molecular weight is about 6500. The UV-Vis and quantum chemical calculation indicate that the different conformation segments named "conformers" exist in the polymer backbones; it was also further confirmed by the single crystal X-ray diffraction study of the dimeric model compound. The π-π^* transition of biphenyl segments of twisted and planar conformations made the polymer exhibit a strong absorption around 256 nm and a weak absorption at about 300 nm. Furthermore, the polymer exhibits a strong UV photoluminescence at 372 nm when the excitation wavelengths are longer than 300 run. The ultraviolet-emitting electroluminescence(EL) device with the single layer structure shows EL λmax of the derivative at 370 nm.展开更多
The morphology and crytal structure of poly(p-phenylene terephthalate) (PPT), prepared by confined thin filmmelt (CTFMP) and solution (CTFSP) and bulk solution polymerization, were characterized by transmission electr...The morphology and crytal structure of poly(p-phenylene terephthalate) (PPT), prepared by confined thin filmmelt (CTFMP) and solution (CTFSP) and bulk solution polymerization, were characterized by transmission electronmicroscopy, electron dimaction and molecular modeling. The unit cell is monoclinic (P2_1/a space group) with parameters a =7.89, b = 5.49, c = 12.65 A, α=γ= 90°, β=100.33°, density = 1.48 g/cm^3, the a, b and β values differing slightly from thosereported previously in the literature. A degree of variation in relative intensities of hk0 reflections in, apparently, untilted[001] ED patterns was observed from a given sample, suggesting some variation in molecular packing. ED evidence wasfound for a second phase, with [001] appearing the same as for phase Ⅱ of the related poly(p-oxybenzoate) (PpOBA)polymer. CTFMP crystals polymerized above 220℃ (up to 370℃) and CTFSP crystals polymerized at 300℃ consisted oflamellae 100-200 A thick.展开更多
A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields.The alkoxy chains(i.e.,n-hex...A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields.The alkoxy chains(i.e.,n-hexyloxy groups) were introduced to assure good solubility of compounds 1-3 in common solvents.The photophysical properties of 1-3 in solution depend strongly on the geometries of these compounds.展开更多
The absorption spectra of the p-phenylene-ethynylene(p-PPE) oligomers(up to n = 12) were estimated by DFT and TD-DFT methods. The effective conjugation length(ECL) of the corresponding polymer was obtained by ex...The absorption spectra of the p-phenylene-ethynylene(p-PPE) oligomers(up to n = 12) were estimated by DFT and TD-DFT methods. The effective conjugation length(ECL) of the corresponding polymer was obtained by extrapolating the first excitation energies of the oligmers to infinite chain length with an alternative exponential function. The absorption spectral red-shift mainly depends on the ?-conjugation segment of oligomers resulting from the planarization of the backbone. The excitation mechanism of the rotamer has been investigated sufficiently by analyzing the orbital density variation upon the conformational rotations around the cylindrical triple-bonded carbon which is believed to impact significantly on the optical spectrum. The calculated results further indicate that rotation about the cylindrical triple bond interrupts the conjugation of rod-like oligomers to lead an angle-dependence of the corresponding excitation energy. The results are helpful to interpret the conformational-dependent spectroscopic phenomena of p-phenyleneethynylene and derivatives oligomers and polymers observed in ensemble and single molecule spectroscopy.展开更多
1, 4-Bis[3-N-propionyl-2-aryl-1, 3, 4-oxadiazoline-5-yl]phenylenes 4 were synthesized by cyclization of corresponding hydrazones 3 with propionic anhydride.
A new process for preparing poly(phenylene sulfide amide, PPSA), which is by reaction of sulfur instead of sodium sulfide as S source with dichlorobenzamide (DCBA) and alkali in polar orga...A new process for preparing poly(phenylene sulfide amide, PPSA), which is by reaction of sulfur instead of sodium sulfide as S source with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure (called sulfur solution route), is reported in the present paper. The influences of polymerization time, molar ratio of precursors, catalyst and solvent upon the polymer were investigated. To seek the best parameters of polymerization, orthogonal design was employed in the experiments. The results indicate that the molar ratio of precursors is the most significant effect on both of viscosity and yield of the polymer. The suitable parameters for preparing the related polymer are presented. The polymer was characterized by IRspectrum, 1HNMRspectrum and Raman spectrum, etc.展开更多
The synthesis of mono- and bis-1,3-diazabicyclo[3.1.0]hex-3-ene derivatives with indole ring and p-phenylene spacer, which behave as photochromic materials, is reported. The structure-photochromic behavior relationsh...The synthesis of mono- and bis-1,3-diazabicyclo[3.1.0]hex-3-ene derivatives with indole ring and p-phenylene spacer, which behave as photochromic materials, is reported. The structure-photochromic behavior relationship (SPBR) of the synthesized compounds has been analyzed.展开更多
The thermal stability of oil gels formed by styrene-butadiene-styrene triblock copolymer (SBS) was improved by adding a small amount of poly(phenylene ether) (PPE), which has a higher glass transition temperature (Tg)...The thermal stability of oil gels formed by styrene-butadiene-styrene triblock copolymer (SBS) was improved by adding a small amount of poly(phenylene ether) (PPE), which has a higher glass transition temperature (Tg). In naphthenic oil which is a good solvent for the butadiene blocks, but a non-solvent for the styrene blocks and PPE, PPE was selectively included into styrene blocks in SBS, and induced the increase of the Tg of these blocks. The melting temperature determined by viscoelastic measurements and softening temperature of the gels were elevated by adding PPE, while no significant change was detected by adding polystyrene. The gel became opaque by adding PPE, and partially separated phases were observed by field emission scanning electron microscopy (FE-SEM). The dependence of the viscoelastic behavior on the PPE concentration can be explained by the structural change observed by FE-SEM.展开更多
When α-ketothioanilide reacts with o-phenylenediamine,there are two competing reactions.One is condensation which forms substituted quinoxaline and the other is substitution which forms substituted quinoxaline-2-thio...When α-ketothioanilide reacts with o-phenylenediamine,there are two competing reactions.One is condensation which forms substituted quinoxaline and the other is substitution which forms substituted quinoxaline-2-thione·By controlling the reaction condition,we can obtain either quinoxaline or quinoxaline-2-thione as the main product.展开更多
Commercial poly(p-phenylene sulfide) (PPS) was thermally cured, which resulted in an increase of molecular weight due to cross-linking. Non-isothermal crystallization studies of samples cured for up to 7 days at 250?C...Commercial poly(p-phenylene sulfide) (PPS) was thermally cured, which resulted in an increase of molecular weight due to cross-linking. Non-isothermal crystallization studies of samples cured for up to 7 days at 250?C showed a monotonous increase of crystallization temperature compared to pure PPS. However, a further increase of curing time decreased the crystallization temperature. The change in the half-crystallization time (t1/2) was similar to the crystallization temperature. Thus, the cross-linking of PPS affected crystallization behaviors significantly. To a certain extent, crosslinks acted as nucleation agents, but excessive cross-linking hindered the crystallization. Morphologies observed by polarized optical microscopy suggested that thermal curing for as little as 1 day contributed to the spherulitic structure having a smaller size, that was not observed with pure PPS.展开更多
基金This work were supported by the National Natural Science Foundation of China (Project No29992530-6) and the Natural Science Foundation of Guangdong Province (Grant No. 990623).
文摘It was found that traces of water in the reaction medium would result in a great increase of gel and a decrease of Molecular weight of the poly(2-methoxy,5-(2'-ethylhexyloxy)-1,4-phenylene vinylene) during the polymerization, which ultimately led to inferior film qualities and device properties. The device (ITO/PEDOT/MEH-PPV/Ba/Al) with MEH-PPV prepared under dry conditions has an external quantum efficiency of above 2.0%.
基金This work was financially supported by the National Natural Science Foundation of China (No. 50473042)the Beijing Natural Science Foundation (No. 2042017).
文摘A novel hyperbranched poly(phenylene oxide) (HPPO) with phenolic terminal groups was prepared from 4-bromo-4',4"-dihydroxytriphenylmethane as AB2 monomer in dimethylsulfoxide (DMSO) via a modified Ullmann reaction. The molecular weight and polydispersity (PD) of the resulting polymers increased with increasing reaction time. In the presence of core molecules (bisphenol A and 1,3,5-trihydroxybenzene), which have the similar molecular backbones to the reactive monomer, the molecular weight could be controlled by varying the core-to-monomer ratio. Incorporation of a very small amount of core molecules could lead to a higher molecular weight as compared with that without the addition of core molecules. However, when the core content reached certain extent, the molecular weight would decrease with the further increase in the core content. A new similar behavior of control over the PD was also obtained. The resulting polymers were characterized by ^1H-NMR, ^13C-NMR, FT-IR, and GPC.
文摘Poly(phenylene sulfide/ether) (PPSE) was synthesized from 4,4'-dihydroxydiphenyl sulfide and 4,4'-dichlorodiphenyl sulfide in solution by nucleophilic substitution reaction. The resulting polymer was characterized by viscosity measurement, elemental analysis, FT-IR, ^1H NMR, X-ray diffraction and thermal analysis. The results showed that the viscosities of the resulting polymer were above 0.68 dL/g, and the linear chain structure of product was confirmed. PPSE had the same reflex indices as poly(p-phenylene sulfide), an orthorhombic crystalline with unit cell a=0.853, b=0.562, c=1.026nm. The melting temperature, glass transition temperature and initial decomposition temperature were found to be 228℃, 85℃ and 325℃, respectively. The product was soluble in common organic solvents such as NMP, N, N'-dimethylformamide, N, N'-dimethylacetamide and 1,2-dichloroethane.
文摘Both aliphatic and aromatic ketones are efficiently transfer-hydrogenated by propan-2-ol under mild conditions in the presence of a catalytic amount of poly(2,6-dimethyl-1,4-Phenylene oxide) (PPO) anchored ruthenium complex and sodium hydroxide. An important feature of this polymer anchored catalyst is its stability in air.
文摘In this work, a quantum-chemical investigation on the structural and opto-electronic properties of oligo(thiophene-phenylene) (4TP) is carried out. The results are discussed in comparison with the properties of corresponding oligothiophene (8T) and oligophenylene (8P). As the opto-electronic properties of this type of conducting polymers are governed by their electronic band gap, we shall also present a comparison among HOMO, LUMO and band gap energies of these three materials.
基金Supported by the Chinese Postdoctoral Foundation.
文摘In this paper the percolation theory is employed to study the insulator-to-conductortransition in sulphonated poly(phenylene oxide)(SPPO) polymer membranes.The membranes withdifferent sulphonation degree were prepared and infrared characterized.The transition thresholdwas calculated by the experimental data of membrane conductivities and the coordination numberwas thus estimated.The functional group-SO<sub>3</sub>H distribution in the membrane was evaluated inaccordance with the calculations and showed a non-random dispersion on the microscopic scale.
基金The authors graefully acknowledge financial support from the National Natural Science Foundation of China (29976040), Natural Science Foundation of Anhui Province (99045431), Key Foundation of Anhui Educational Comrnittee (2000j1255zd), the Foundation of
文摘This paper investigates the possibility of attaining sulphonated poly(phenylene oxide) (SPPO) with a relativelyhigher sulfonation degree. To achieve this aim, the approach we adopt is to improve the solubility of the final product in themixed solvent so that the sulfonation may take place between the bulk solutions and PPO powders even at higher sulfonationdegree. It is shown that the addition of a proper amount of dimethyl formide (DMF) to the conventional PPO-chloroformsystem can actually enhance the sulfonation effect. The solvent composition is then correlated with the sulfonation degreebased on the solubility parameters. It is interesting to find that solubility parameters between the mixed solvent and theprecipitated products keep an approximately unchanged value at about 4.9, which is just equal to that when pure chloroformis used, though the solubility parameters of both solvents increase with the content of DMF in solution. This may be the mainreason why the addition of DMF can reduce the precipitation and improve the ion exchange capacity (IEC) of SPPOpolymer.
文摘The apparent solubility (S), concentration-average diffusivity (D), and permeability (P), for C0_2, CH_4 and N_2 through PPO and aryl-brominated PPO at 35℃ for pressure ranging from 1 to 26 atm are reported. It is found that P, D, and S of the membranes to all the three gases vary with the extent of bromination. S increases with the increase of the percent of bromine in each case, but D to CO_2 increases remarkably only at higher degree of brominafion, and therefore, P to CO_2 is increased by more than 100% over a wide range ofpressure in the case. The solubility data are well described by the dual mode sorption model. It is found that the gas molecules sorbed by the Langmuir mode are relatively more immobilized and the contribution of the nonequilibrinm character of the polymer to gas permeation increases obviously for CO_2 and is hardly changed for CH_4 with increasing bromine content. These observations are interpreted in terms of changes in specific free volume (SFV)and the cohesive energy density (CED) of the polymers.
文摘Poly(phenylene sulfide amide) (PPSA) has been synthesized by using sulfur as S source which reacts with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure. The polymer structures were determined by elemental analysis, FT-IR and H-1-NMR. It is shown that the yielded polymer has linear structure and its structure unit is -p-C6H4-CONH -p-C6H4-S-. The polymer morphology was studied by X-ray diffraction and polarized microscopy. The results show that PPSA is a crystalline polymer and its spherulites are the aggregation of nontwisting lamella or micro-thread structure. Under shearing force, these crystals are dispersed to form micro-fibrillar structure. The decomposition kinetics of PPSA was also studied at different heating rates. The decomposition energy of PPSA is higher than that of PPS.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.10804064 and 10674084)
文摘A first-principles computational method based on the hybrid density functional theory is developed to simulate the electronic transport properties of oligomeric phenylene ethynylene molecular junctions with H2O molecules accumulated in the vicinity as recently reported by Na et al. [Nanotechnology 18 424001 (2007)]. The numerical results show that the hydrogen bonds between the oxygen atoms of the oligomeric phenylene ethynylene molecule and H2O molecules result in the localisation of the molecular orbitals and lead to the lower transition peaks. The H2O molecular chains accumulated in the vicinity of the molecular junction can not only change the electronic structure of the molecular junctions, but also open additional electronic transport pathways. The obvious influence of H2O molecules on the electronic structure of the molecular junction and its electronic transport properties is thus demonstrated.
基金Supported by the National Natural Science Foundation of China(Nos.20125421,90101026,50303007,20474024 and 50473001)Ministry of Science and Technology of China(No.2002CB6134003).
文摘A soluble poly(meta-phenylene) derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction. The polymer is soluble in common organic solvents, and the number-average molecular weight is about 6500. The UV-Vis and quantum chemical calculation indicate that the different conformation segments named "conformers" exist in the polymer backbones; it was also further confirmed by the single crystal X-ray diffraction study of the dimeric model compound. The π-π^* transition of biphenyl segments of twisted and planar conformations made the polymer exhibit a strong absorption around 256 nm and a weak absorption at about 300 nm. Furthermore, the polymer exhibits a strong UV photoluminescence at 372 nm when the excitation wavelengths are longer than 300 run. The ultraviolet-emitting electroluminescence(EL) device with the single layer structure shows EL λmax of the derivative at 370 nm.
基金This research was supported, in part, by grants from the National Science Foundation (NSF-DMR Intemational Program 96-16255 (F. R. and P. H. G.) and NSF-DMR Polymer Program 93-12823 and 96-16255 (J. Y., G. S., J. L. and P. H. G.)) and Grant Agency of the
文摘The morphology and crytal structure of poly(p-phenylene terephthalate) (PPT), prepared by confined thin filmmelt (CTFMP) and solution (CTFSP) and bulk solution polymerization, were characterized by transmission electronmicroscopy, electron dimaction and molecular modeling. The unit cell is monoclinic (P2_1/a space group) with parameters a =7.89, b = 5.49, c = 12.65 A, α=γ= 90°, β=100.33°, density = 1.48 g/cm^3, the a, b and β values differing slightly from thosereported previously in the literature. A degree of variation in relative intensities of hk0 reflections in, apparently, untilted[001] ED patterns was observed from a given sample, suggesting some variation in molecular packing. ED evidence wasfound for a second phase, with [001] appearing the same as for phase Ⅱ of the related poly(p-oxybenzoate) (PpOBA)polymer. CTFMP crystals polymerized above 220℃ (up to 370℃) and CTFSP crystals polymerized at 300℃ consisted oflamellae 100-200 A thick.
基金Beijing Natural Science Foundation(No.2093033)Scientific Research Project of Beijing Educational Committee(No.KM200910020012) for financial support.
文摘A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields.The alkoxy chains(i.e.,n-hexyloxy groups) were introduced to assure good solubility of compounds 1-3 in common solvents.The photophysical properties of 1-3 in solution depend strongly on the geometries of these compounds.
基金supported by the National Natural Science Foundation of China(21373012)the Key Project of Educational Committee of Anhui Province(KJ2010A143)
文摘The absorption spectra of the p-phenylene-ethynylene(p-PPE) oligomers(up to n = 12) were estimated by DFT and TD-DFT methods. The effective conjugation length(ECL) of the corresponding polymer was obtained by extrapolating the first excitation energies of the oligmers to infinite chain length with an alternative exponential function. The absorption spectral red-shift mainly depends on the ?-conjugation segment of oligomers resulting from the planarization of the backbone. The excitation mechanism of the rotamer has been investigated sufficiently by analyzing the orbital density variation upon the conformational rotations around the cylindrical triple-bonded carbon which is believed to impact significantly on the optical spectrum. The calculated results further indicate that rotation about the cylindrical triple bond interrupts the conjugation of rod-like oligomers to lead an angle-dependence of the corresponding excitation energy. The results are helpful to interpret the conformational-dependent spectroscopic phenomena of p-phenyleneethynylene and derivatives oligomers and polymers observed in ensemble and single molecule spectroscopy.
文摘1, 4-Bis[3-N-propionyl-2-aryl-1, 3, 4-oxadiazoline-5-yl]phenylenes 4 were synthesized by cyclization of corresponding hydrazones 3 with propionic anhydride.
文摘A new process for preparing poly(phenylene sulfide amide, PPSA), which is by reaction of sulfur instead of sodium sulfide as S source with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure (called sulfur solution route), is reported in the present paper. The influences of polymerization time, molar ratio of precursors, catalyst and solvent upon the polymer were investigated. To seek the best parameters of polymerization, orthogonal design was employed in the experiments. The results indicate that the molar ratio of precursors is the most significant effect on both of viscosity and yield of the polymer. The suitable parameters for preparing the related polymer are presented. The polymer was characterized by IRspectrum, 1HNMRspectrum and Raman spectrum, etc.
文摘The synthesis of mono- and bis-1,3-diazabicyclo[3.1.0]hex-3-ene derivatives with indole ring and p-phenylene spacer, which behave as photochromic materials, is reported. The structure-photochromic behavior relationship (SPBR) of the synthesized compounds has been analyzed.
文摘The thermal stability of oil gels formed by styrene-butadiene-styrene triblock copolymer (SBS) was improved by adding a small amount of poly(phenylene ether) (PPE), which has a higher glass transition temperature (Tg). In naphthenic oil which is a good solvent for the butadiene blocks, but a non-solvent for the styrene blocks and PPE, PPE was selectively included into styrene blocks in SBS, and induced the increase of the Tg of these blocks. The melting temperature determined by viscoelastic measurements and softening temperature of the gels were elevated by adding PPE, while no significant change was detected by adding polystyrene. The gel became opaque by adding PPE, and partially separated phases were observed by field emission scanning electron microscopy (FE-SEM). The dependence of the viscoelastic behavior on the PPE concentration can be explained by the structural change observed by FE-SEM.
文摘When α-ketothioanilide reacts with o-phenylenediamine,there are two competing reactions.One is condensation which forms substituted quinoxaline and the other is substitution which forms substituted quinoxaline-2-thione·By controlling the reaction condition,we can obtain either quinoxaline or quinoxaline-2-thione as the main product.
文摘Commercial poly(p-phenylene sulfide) (PPS) was thermally cured, which resulted in an increase of molecular weight due to cross-linking. Non-isothermal crystallization studies of samples cured for up to 7 days at 250?C showed a monotonous increase of crystallization temperature compared to pure PPS. However, a further increase of curing time decreased the crystallization temperature. The change in the half-crystallization time (t1/2) was similar to the crystallization temperature. Thus, the cross-linking of PPS affected crystallization behaviors significantly. To a certain extent, crosslinks acted as nucleation agents, but excessive cross-linking hindered the crystallization. Morphologies observed by polarized optical microscopy suggested that thermal curing for as little as 1 day contributed to the spherulitic structure having a smaller size, that was not observed with pure PPS.