一种耐高温氟化聚二氮杂萘酮芳醚憎水材料的合成及性能

SYNTHESIS AND PROPERTIES OF A WATER-REPELLENT FLUORINATED POLY(PHTHALAZINONE ETHER)

由五氟苯肼和2-(4-羟基苯甲酰)苯甲酸制备了AB-型双官能团单体4-(4-羟基苯基)-2-五氟苯基-二氮杂萘酮,以苯做带水剂,在K2CO3的催化下温和的反应条件下通过自身亲核缩聚反应合成了结构规整的氟化聚二氮杂萘酮芳醚材料.用傅里叶衰减全反射红外光谱(FTIR ATR)、氢谱(1H-NMR)、氟谱(19F-NMR)对材料的结构进行了表征.该聚合物的玻璃化转变温度Tg为316℃,Td,5 wt%为491℃,具有良好的热性能;该聚合物薄膜样品测试结果表明该材料具有高的力学性能和绝缘性,拉伸强度超过了60 MPa,表面电阻率为1.8×1015Ω/m2,体积电阻率为5.6×1012Ω/m3;该聚合物在DMAc,DMF,DMSO,NMP,1,1,2,2-四氯乙烷,四氢呋喃,氯仿,吡啶和环丁砜中有良好的溶解性,可加工得到光滑、硬韧的膜;利用表面接触角测定仪考察了不同溶剂体系所得膜材料的表面性能,用DMAc制备膜的接触角为93.3°,用氯仿制备膜的接触角为92.5°,用THF制备膜的接触角为127.1°,接触角大于聚四氟乙烯(112°),且所有考察溶剂中所得膜的接触角都大于90°,具有较好的憎水性.

The objective of this work was to develop a kind of new poly （phthalazinone ether） with high hydrophobicity,good thermal stabilities and excellent mechanical properties. The introduction of fluorine into poly（phthalazinone ether） is regarded as an effective way. A fluorinated poly（phthalazinone ether） containing tetrafluorophenyl groups was successfully synthesized by aromatic nucleophilic substituting self- polycondensation from AB type phthalazinone monomer 4-（4-hydroxyphenyl）-2-（pentafluorophenyl） phthalazin-1 （2H）-one at 100℃. The structure of the polymer was characterized by FTIR ATR,1H-NMR and 19F-NMR. Number average molecular weight characterized by GPC was 1.53× 10^4Da. The DSC and TGA measurements of the polymer were performed under a nitrogen atmosphere, and the results showed that the polymer exhibited good thermal stabilities with high Tg of 316℃ and 5% mass loss at 491℃. Moreover, the polymer was soluble in common organic solvents, such as DMAc, DMF, DMSO, NMP, TCE, THF, chloroform, pyridine and sulpholane,and could be readily cast into tough and smooth films from solutions. The films also showed high contact angles of water. Contact angle of the film cast by DMAc is 93.3 °. Contact angle of the film cast by CHC13 is 92.5°. Contact angle of the film cast by THF is 127. 1°, which is higher than that of polytetrafluoroethylene （ 112°） , indicating that the polymer has high hydrophobicity. Tension test results of film samples indicated the polymer demonstrated excellent mechanical properties with tensile strength over 60 MPa. The polymer exhibited good insulating properties with electrical surface resistivity of 1.8×1015Ω/m2 and volume resistivity of 5.6×1012Ω/m3. The synthesized polymer may have a promising prospect in microelectronic devices, such as the substrate for printed boards and insulating materials as interlayer dielectrics and intermetal dielectrics.