联苯胺类共轭共聚物的金属配合物催化法合成及性质

PREPARATION OF POLYBENZIDINE TYPE π-CONJUGATED COPOLYMERS WITH A METAL NICKEL COMPLEX AS CATALYST AND THEIR PROPERTIES

联苯二胺 ,3,3′ 二甲基联苯二胺在次氯酸钠介质中氧化制备了相应的N ,N′ 二氯联苯醌二亚胺 ,3,3′ 二甲基 N ,N′ 二氯联苯醌二亚胺 .通过红外 (FT IR) ,核磁共振 (1 H NMR)等进行了表征 .研究了此化合物在二价镍配合物存在下 ,与 2 ,5 二溴噻吩制成的Grignard试剂共聚的方法 ,并得到了联苯醌二亚胺与噻吩交替共聚的共轭聚合物 .该合成方法所得聚合物的纯收率分别为 6 3% ,88% .循环伏安测定表明该类聚合物具有一定的电化学活性 ,紫外 可见光谱中分别在 310nm ,4 5 0nm处 (共聚物Ⅰ )和 2 90nm ,4 30nm处 (共聚物Ⅱ )出现吸收峰 .根据聚合物的粉末X 射线衍射图 (XRD) ,对所得聚合物的结晶性也做了初步探讨 .

New alternative π conjugated copolymers were obtained by nickel(Ⅱ) complex catalyzed polycodensation of N,N ′ dichlorodiphenoquinonediimine or 3,3′ dimethyl N,N ′ dichlorodipheno quinone diimine with 2,5 thiophenylene dimagnesium dibromide.The monomers were prepared from the corresponding benzidines oxidized by NaOCl.The monomers were characterized by FT IR and 1H NMR. The copolymers were characterized by FT IR,UV Vis, cyclic voltammogram and XRD.The obtained copolymers were partially soluble in DMF,DMSO and CF\-3COOH.The soluble part (in DMSO) of copolymer Ⅱ showed two absorption peaks at about 310 nm and 450 nm,respectively,while copolymer Ⅰ showed two absorption peaks at about 290 nm and 430 nm,respectively.The results from cyclic voltammogram and XRD showed that the copolymers had electrochemical activity,and the copolymers were amorphous.