以己二胺为原料利用界面反应制备了双氟酰胺单体1,6-N,N′-双(4-氟苯甲酰胺)己烷(BFBH),并与硫化钠、二氯二苯砜通过溶液缩聚制备了一系列新型半芳族聚酰胺共聚改性聚芳硫醚砜(Semi-PASS/A)树脂。通过核磁氢谱(1 H NMR)和红外光谱(FTIR...以己二胺为原料利用界面反应制备了双氟酰胺单体1,6-N,N′-双(4-氟苯甲酰胺)己烷(BFBH),并与硫化钠、二氯二苯砜通过溶液缩聚制备了一系列新型半芳族聚酰胺共聚改性聚芳硫醚砜(Semi-PASS/A)树脂。通过核磁氢谱(1 H NMR)和红外光谱(FTIR)表征了单体及聚合物的化学结构。结果表明,新型单体及聚合物成功制备。Semi-PASS/A树脂的特性黏度范围为0.43~0.55 dL/g,该共聚物具有优异的热性能,其玻璃化转变温度范围为202~215℃,5%热分解温度范围为396~429℃。玻璃化转变温度、热分解温度均随着聚合物中半芳族酰胺含量的增加而下降。平板流变结果表明,Semi-PASS/A的复数黏度相比于聚芳硫醚砜树脂(PASS)下降显著,PASS树脂的25470 Pa·s降低至Semi-PASS/A-10树脂(BFBH的摩尔分数为10%)的36.9 Pa·s。随着半芳族聚酰胺含量的增加,共聚物的复数黏度降低。此外,Semi-PASS/A树脂在高温(310℃)下的时间测试中,其熔体复数黏度随时间增加基本保持稳定,表明半芳族聚酰胺引入PASS树脂结构中不仅降低了聚合物的熔体黏度,同时还有效改善了PASS的熔体稳定性,极大地改善了PASS的熔体加工性能。展开更多
A new biphenol-like monomer,4,4′-methylenebis[4-(1,4-phenylene)-phthalazin-1(2H)-one] was synthesized from phthalic anhydride and diphenylmethane in two steps.In the first step,Friedel-Crafts reaction was carried out...A new biphenol-like monomer,4,4′-methylenebis[4-(1,4-phenylene)-phthalazin-1(2H)-one] was synthesized from phthalic anhydride and diphenylmethane in two steps.In the first step,Friedel-Crafts reaction was carried out in 1,2-dichloroethane between diphenylmethane and phthalic anhydride.The obtained product was used in the second step with hydrazine monohydrate added into its solution,followed by recrystallization in acetic acid.The melting point showed by differential scanning calorimetry of the bis(phthalazinone) monomer was 338.1℃.The overall yield of the biphenol-like monomer was 60%.A new polyphthalazinone was prepared from 4,4′-difluorodiphenylketone(DFK) and 4,4′-methylenebis[4-(1,4-phenylene)-phthalazin-1(2H)-one] by solution polycondensation in N-methyl-2-pyrrolidone(NMP) with anhydrous K 2CO 3 as a catalyst.High molecular weight polymer was formed in 8 h at 190℃.The polymer was refined by precipitation from its 15% NMP solution with methanol as the precipitating agent.The powder of the polymer was dried in a vacuum oven under 120℃ for 48*!h and then under 200℃ for 4*!h.The intrinsic viscosity of the polymer was 0.58*!dL/g in NMP at 25℃.The polymer showed high glass transition temperature (T g) at 258℃ by DSC.The decomposition temperature for 5% weight loss (T d5) in nitrogen measured by thermogravimetric analysis occurred at 431℃.The solubility of the polymer was investigated at room temperature.The polymer was soluble in NMP,m-cresol and partially soluble in chloroform,and insoluble in N,N-dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO).The methylene group and bis-(phthalazinone) structure in the backbone of the polymer contribute much to the good solubility,and the rigid structure of bis(phthalazinone) retains its good thermal properties.展开更多
文摘A new biphenol-like monomer,4,4′-methylenebis[4-(1,4-phenylene)-phthalazin-1(2H)-one] was synthesized from phthalic anhydride and diphenylmethane in two steps.In the first step,Friedel-Crafts reaction was carried out in 1,2-dichloroethane between diphenylmethane and phthalic anhydride.The obtained product was used in the second step with hydrazine monohydrate added into its solution,followed by recrystallization in acetic acid.The melting point showed by differential scanning calorimetry of the bis(phthalazinone) monomer was 338.1℃.The overall yield of the biphenol-like monomer was 60%.A new polyphthalazinone was prepared from 4,4′-difluorodiphenylketone(DFK) and 4,4′-methylenebis[4-(1,4-phenylene)-phthalazin-1(2H)-one] by solution polycondensation in N-methyl-2-pyrrolidone(NMP) with anhydrous K 2CO 3 as a catalyst.High molecular weight polymer was formed in 8 h at 190℃.The polymer was refined by precipitation from its 15% NMP solution with methanol as the precipitating agent.The powder of the polymer was dried in a vacuum oven under 120℃ for 48*!h and then under 200℃ for 4*!h.The intrinsic viscosity of the polymer was 0.58*!dL/g in NMP at 25℃.The polymer showed high glass transition temperature (T g) at 258℃ by DSC.The decomposition temperature for 5% weight loss (T d5) in nitrogen measured by thermogravimetric analysis occurred at 431℃.The solubility of the polymer was investigated at room temperature.The polymer was soluble in NMP,m-cresol and partially soluble in chloroform,and insoluble in N,N-dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO).The methylene group and bis-(phthalazinone) structure in the backbone of the polymer contribute much to the good solubility,and the rigid structure of bis(phthalazinone) retains its good thermal properties.
