A novel unsymmetrical dianhydride containing 4\|(4\|hydroxylphenyl)\|2,3\|phthalazin\|1\|one was synthesized in order to improve the solubility of aromatic polyimides according to the principle of designing new monome...A novel unsymmetrical dianhydride containing 4\|(4\|hydroxylphenyl)\|2,3\|phthalazin\|1\|one was synthesized in order to improve the solubility of aromatic polyimides according to the principle of designing new monomers.This article reported a series of polyimide random copolymers derived from 4,4′ diamino diphenyl sulfone (DAPS),4,4′ oxyl dianiline (ODA) and the new dianhydride\|2 (3,4 dicarboxyl phenyl) 4 (3′,4′ dicarboxyl phenyl oxyl) phenyl 2,3 phthalazine 1 one dianhydride (DAH4) by“one step”solution polycondensation in m cresol with catalystic amount of isoquinoline at 200℃.Some properties of the copolymers were investigated by DSC,TG and mechanical analysis.The result shows that the η inh of copolymers is between 0 64 to 0 71 dL/g in m cresol at 25℃,and the T g of the copolymers are higher than that of pure poliymides containing 4,4′ oxyl dianiline (polymer 5).The relationship between T g and mole percent of DAPS is not obvious.Degradation temperature for 5% weight loss ( T d5 ) of the copolymers occurs all above 470℃ in air.The mechanical properties of the copolymers are lower owing to introducing sulfone groups into polymer’s backbone.In sharp contrast,the copolymers have good solubility and can be easily soluble in 1,1,2,2 tetrachloroethane(TCE), N,N dimethylacetamide(DMAc), N methyl 2 pyrrolidinone (NMP), m cresol and pyridine.Furthermore,the copolymers have better solubility in dimethyl sulfoxide (DMSO) and chloroform than the polyimide derived from DAH4 and ODA.展开更多
Starting from an initial sample of butene-1/ethylene copolymer with stable form I＇, we examined the nucleation of different crystalline polymorphs （here metastable form II and stable form I＇） at different isother...Starting from an initial sample of butene-1/ethylene copolymer with stable form I＇, we examined the nucleation of different crystalline polymorphs （here metastable form II and stable form I＇） at different isothermal crystallization temperatures after being melted at different melt temperature （Tmelt）. When Tmelt was just above the melting temperature （Tm） of the crystallites, self-seeding took place. There, residue crystallites served as nuclei leading to the crystallization of the same crystalline phase. When Tmelt was a few degrees above the Tin, self-seeding was disabled due to complete melting of the initial crystals. Upon crystallization, the selection of the different polymorphs in this random copolymer was found to depend on an interplay between the domain size of segregated long crystallizable sequences and the size and energy barrier of the critical nucleus of the respective crystalline forms. Our results provide a clear understanding of the polymorphs selection during crystallization of a random copolymer as well as homo-polymers under confinement.展开更多
文摘A novel unsymmetrical dianhydride containing 4\|(4\|hydroxylphenyl)\|2,3\|phthalazin\|1\|one was synthesized in order to improve the solubility of aromatic polyimides according to the principle of designing new monomers.This article reported a series of polyimide random copolymers derived from 4,4′ diamino diphenyl sulfone (DAPS),4,4′ oxyl dianiline (ODA) and the new dianhydride\|2 (3,4 dicarboxyl phenyl) 4 (3′,4′ dicarboxyl phenyl oxyl) phenyl 2,3 phthalazine 1 one dianhydride (DAH4) by“one step”solution polycondensation in m cresol with catalystic amount of isoquinoline at 200℃.Some properties of the copolymers were investigated by DSC,TG and mechanical analysis.The result shows that the η inh of copolymers is between 0 64 to 0 71 dL/g in m cresol at 25℃,and the T g of the copolymers are higher than that of pure poliymides containing 4,4′ oxyl dianiline (polymer 5).The relationship between T g and mole percent of DAPS is not obvious.Degradation temperature for 5% weight loss ( T d5 ) of the copolymers occurs all above 470℃ in air.The mechanical properties of the copolymers are lower owing to introducing sulfone groups into polymer’s backbone.In sharp contrast,the copolymers have good solubility and can be easily soluble in 1,1,2,2 tetrachloroethane(TCE), N,N dimethylacetamide(DMAc), N methyl 2 pyrrolidinone (NMP), m cresol and pyridine.Furthermore,the copolymers have better solubility in dimethyl sulfoxide (DMSO) and chloroform than the polyimide derived from DAH4 and ODA.
基金financially supported by the National Natural Science Foundation of China(Nos.21134006 and 51525305)
文摘Starting from an initial sample of butene-1/ethylene copolymer with stable form I＇, we examined the nucleation of different crystalline polymorphs （here metastable form II and stable form I＇） at different isothermal crystallization temperatures after being melted at different melt temperature （Tmelt）. When Tmelt was just above the melting temperature （Tm） of the crystallites, self-seeding took place. There, residue crystallites served as nuclei leading to the crystallization of the same crystalline phase. When Tmelt was a few degrees above the Tin, self-seeding was disabled due to complete melting of the initial crystals. Upon crystallization, the selection of the different polymorphs in this random copolymer was found to depend on an interplay between the domain size of segregated long crystallizable sequences and the size and energy barrier of the critical nucleus of the respective crystalline forms. Our results provide a clear understanding of the polymorphs selection during crystallization of a random copolymer as well as homo-polymers under confinement.
