低介电聚(酰亚胺-苯并噁唑)用含氟二胺单体的制备与表征

Preparation and Characterization of Fluoro-containing Diamine Monomers for Low-dielectric Poly(imide-benzoxazole)s

针对高频通讯技术的发展对于具有低介电常数(low-Dk)以及低介质损耗因数(low-Df)型耐高温聚合物介质材料的应用需求,开展了含氟型聚(酰亚胺-苯并噁唑)(PIBO)用关键芳香族二胺单体,包括2,2-双[3-(4-胺基苯甲酰胺)-4-羟基苯基]六氟丙烷(p6FAHP)与2,2-双[3-(3-胺基苯甲酰胺)-4-羟基苯基]六氟丙烷(m6FAHP)的合成研究。采用硝基取代苯甲酰氯与2,2-双[(3-胺基-4-羟基)苯基]六氟丙烷(6FAP)在极性非质子性溶剂中低温反应,首先合成了分子结构中含有双(邻羟基取代苯甲酰胺)基团的二硝基化合物,然后在Pd/C催化下采用氢气还原得到了二胺基化合物。采用差示扫描量热分析(DSC)手段测试两种二胺单体的熔点,并采用衰减全反射傅里叶红外光谱(ATR-FTIR)、核磁(NMR)以及元素分析(EA)等手段表征二胺单体的化学结构。结果成功制得了预期结构的芳香族二胺单体。

According to the application requirements of high-temperature resistant polymers with low dielectric constant(low-Dk)and low dielectric loss factor(low-Df)for the development of high frequency communication technology,two key diamine monomers for fluoro-containing poly(imide-benzoxazole)s(PIBO),including 2,2-bis[3-(4-aminobenzamide)-4-hydroxylphenyl]hexafluoropropane(p6FAHP)and 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane(m6FAHP)were synthesized.The dinitro compounds containing bis(o-hydroxy substituted benzamide)groups in molecular structure were first prepared by the low temperature reactions of the nitro-substituted benzoyl chloride and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro-propane(6FAP)in polar aprotic solvent.Then the diamine monomers were obtained by the reduction of hydrogen under the catalysis of Pd/C.The melting points of the diamines were measured by DSC.The chemical structures of the diamines were characterized by ATR-FTIR,NMR,and elemental analysis(EA).The results show that the aromatic diamine monomers with expected structures are prepared successfully.