二苯胺-4-偶氮磺酸盐及其树脂的制备和光、热分解性质

PREPARATION OF DIPHENYLAMINE-4-DIAZOSULFONATES,DIAZOSULFONATE RESINS,AND THEIR PHOTOCHEMICAL,THERMAL DECOMPOSITION

从二苯胺 4 重氮盐(DS)和3 甲氧基二苯胺 4 重氮盐(MDS)以及重氮树脂(DR)和硝基重氮树脂(NDR)与亚硫酸钠反应,在水溶液中制备了相应的二苯胺 4 偶氮磺酸盐DSS和MDSS(简称偶氮磺酸盐)及相应的重氮树脂的偶氮磺酸盐DRS和NDRS(简称偶氮磺酸盐树脂).对它们在水溶液和固相膜中的光、热反应进行了研究.结果表明偶氮磺酸盐与偶氮磺酸盐树脂有很好的感光性能,而热稳定性比相应的重氮盐和重氮树脂好很多,其中二苯胺上有硝基取代的偶氮磺酸盐树脂具有突出的热稳定性,其水溶液在70℃加热6h,其固相膜在100℃加热11天几乎观察不到分解.对偶氮磺酸盐及偶氮磺酸盐树脂的光、热分解机理作了初步分析.

Four diphenylamine4diazosulfonates:DSS,MDSS,DRS,NDRS derived from diphenylamine4diazonium salt(DS),3methoxydiphenylamine4diazonium salt(MDS),diazoresin(DR)and nitro substituted diazoresin(NDR) were prepared via the reactions of Na2SO3 and corresponding diazonium salts or diazoresins.The photochemical and thermal decomposition of these compounds in aqueous solution or in solid film(or in coating)have been investigated and confirmed that the photochemical decomposition of this kind of diazosulfonates is rather fast and the thermal stability is much better than the corresponding diazonium salts and diazoresins.Among them the NDRS exhibits the best thermal stability with almost no considerable decomposition both in aqueous solution heated for 6 h at 70 ℃ and in solid film heated for 11 days at 100 ℃.A mechanism of the photo as well as the thermal decomposition for this kind of diazosulfonates has been proposed tentatively.