主链含邻位取代单元及吡啶环聚酰亚胺的合成与性能  

SYNTHESIS AND PROPERTIES OF POLYIMIDE CONTAINING ORTHO-LINKED UNITS AND PYRIDINE MOIETIES

作　　者：黄明富[1] 王丽[1] 沈杰[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 [2]功能材料绿色制备与应用省部共建教育部重点实验室,武汉430062

出　　处：《高分子学报》2012年第6期613-620,共8页Acta Polymerica Sinica

基　　金："十一五"国家科技重点支持计划(项目号2008BAC32B03)项目资助

摘　　要：以o-羟基苯乙酮、对氯硝基苯和苯甲醛为原料,通过亲核取代反应、改进的Chichibabin反应以及水合肼催化还原合成了一种新型含邻位取代单元及吡啶环的芳香二胺4-苯基-2,6-双[3-(4-氨基苯氧基)苯基]吡啶(o,p-PAPP).以N,N-二甲基甲酰胺(DMF)为溶剂,将o,p-PAPP分别与3,3',4,4'-二苯醚四羧酸二酐(ODPA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA)、3,3',4,4'-二苯酮四甲酸二酐(BTDA)及均苯四甲酸二酐(PMDA)通过常规的两步法,合成了4种聚酰亚胺.用FTIR、DSC、TGA、XRD、溶解性测试、UV-Vis和荧光光谱对聚合物的结构和性能进行了表征.FTIR结果表明,所得的聚合物在1780,1720和1380cm-1左右出现了聚酰亚胺的特征吸收峰.实验所得的PI能很好地溶解于常见有机溶剂(如DMF,DMAC,DMSO,NMP,THF,CHCl3),在氮气氛中,PI的10%失重温度(T10)为444.2～467.5℃,800℃时的残余质量(Rw)为49.6%～58.3%.同时PI分子主链中的吡啶环结构使其具有良好的紫外光吸收性能,经HCl质子化后,在460 nm附近出现非常强的荧光发射峰.A novel pyridine-containing aromatic diamine monomer, 4-[4-phenyl]-2, 6-bis [ 4-（ 2- aminophenoxy） phenyl ] pyridine （p, o-PAPP） was successfully synthesized respectively by nucleophilic substitution reaction, modified Chichibabin reaction and catalytic reduction with hydrazine monohydrate, 2- hydroxyacetophenone and benzaldehyde. The aromatic diamine was employed to prepare a series of pyridine- containing polyimides by polyeondensation with various aromatic dianhydrides in N, N-dimethylformamide （DMF） via the conventional two-step method. The inherent viscosities of the resulting poly （ amic acid） s （PAAs） and polyimides （PIs） were in the range of 0.59 - 0.73 and 0.52 - 0.63 dL/g, respectively. The structure and performance of polymers were characterized by FTIR, solubility testing, DSC, XRD,TGA, UV-Vis and fluorescence spectroscopy. The results showed that there were characteristic peaks of polyimide around 1780,1720 and 1380 cm-1 in the FTIR spectra. The obtained PIs exhibited high solubility in common organic solvents, such as m-cresol, DMF, N, N-dimethylacetamide （DMAc）, dimethylsulfoxide （DMSO）, N- methylpyrrolidone （ NMP）, tetrahydrofuran （THF） and chloroform （ CHCl3 ）. Meanwhile, flexible PI films were obtained,which had excellent thermal stability with the glass transition temperature （Ts） of 162.2 - 195.2℃ and the temperature at 10% weight loss of 444.2 -467.5℃ in nitrogen atmosphere. The protonated polymer showed UV-Vis absorption in the region 200 - 360 nm and displayed strong fluorescence intensity （460 nm） in THF solution.

关 键 词：聚酰亚胺 二胺 荧光 吡啶 设计 

分 类 号：O633.22[理学—高分子化学]