新型含吡啶环二胺及其可溶透明性氟化聚酰亚胺的合成与表征  

Optically transparent and highly soluble fluorinated polyimide derived from novel pyridine-containing diamine

作　　者：颜善银[1] 黄明富[1] 陈川[1] 舒亚莎[1] 周嘉珊[1] 徐祖顺[1,2] 易昌凤[1,2] 

机构地区：[1]湖北大学材料科学与工程学院,湖北武汉430062 [2]功能材料绿色制备与应用省部共建教育部重点实验室,湖北武汉430062

出　　处：《合成技术及应用》2010年第3期5-11,共7页Synthetic Technology & Application

基　　金：湖北省自然科学基金项目(2008CDB276)

摘　　要：以4-三氟甲基苯甲醛和3-(4-硝基苯氧基)苯乙酮(m,p-NPAP)为原料,通过改进的Chichibabin反应制备了硝基化合物4-(4-三氟甲基苯基)-2,6-双[3-(4-硝基苯氧基)苯基]吡啶(m,p-3FPNPP),再用Pd/C和水合肼将m,p-3FPNPP进行还原,成功制备了一种新型含吡啶环的芳香二胺4-(4-三氟甲基苯基)-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(m,p-3FPAPP)。以m,p-3FPAPP作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,经热或者化学亚胺化形成聚酰亚胺,制得了一种新型的含吡啶环聚酰亚胺。所得聚酰胺酸和聚酰亚胺的粘度分别为0.78 dL/g和0.65 dL/g。化学亚胺化所得的聚酰亚胺速溶于常见有机溶剂如DMF、N,N-二甲基乙酰胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、四氢呋喃(THF)等。制得了柔韧的聚酰亚胺膜,膜有很好的热稳定性,玻璃化转变温度(Tg)为234.4℃,氮气氛中10%失重温度为575.3℃,膜有很好的光学透明性,截止波长为369 nm,同时,膜还有较好的力学性能,拉伸强度为96.4 MPa,拉伸模量为1.63 GPa,断裂伸长率为9.2%,膜的吸水率为0.68%。A novel pyridine-containing aromatic diamine monomer ,4- （ 4-trifluoromethylphenyl ） -2,6-bis [ 3- （ 4- aminophenoxy） phenyl ] pyridine （m,p-3FPAPP）, was successfully synthesized by a modified Chichibabin reaction of 4-trifluoromethylbenzaldehyde and a substituted acetophenone, 3- （4-nitrophenoxy） acetophenone （ m ,p-NPAP）, followed by a reduction of the resulting dinitro compound 4- （ 4-trifluoromethylphenyl ） -2,6- bis [ 3 - （ 4-nitrophenoxy ） phenyl] pyridine （m,p-3FPNPP） with Pd/C and hydrazine monohydrate. The aromatic diamine was employed to synthesize a new pyridine-eontaining polyimide by polycondensation with 4,4＇-Oxydiphthalic dianhydride （ODPA） in N, N-dimethyllformamide （DMF） via the conventional two-step method, and further thermal or chemical irnidization forming polyimide. The inherent viscosities of the resulting poly （ amic acid） and polyimide were 0. 78 dL/g and 0. 65 dL/g, and the polyimide obtained by chemical imidization was readily soluble in common organic solvents such as DMF , N, N-dimethylacetamide （ DMAc ）, N-methyl-2-pyrrolidone （ NMP）, and tetrahydrofuran （ THF）, etc. Meanwhile, strong and flexible polyimide film was obtained, which had good thermal stability, with the glass transition temperature （ Tg ） of 234.4 ℃ and the temperature at 10% weight loss of 575.3℃ in nitrogen atmosphere, and good optical transparency with the cut-off wavelengths of 369 nm, as properties with tensile strengths of 96. 4 MPa, a tensile modulus of 1.63 GPa and The polyimide film also was found to possess low water uptake of 0. 68%.

关 键 词：含吡啶环二胺 氟化聚酰亚胺 溶解性 透明性 热性能 

分 类 号：O631.5[理学—高分子化学] TQ323.7[理学—化学]