相转移反应合成聚[α,γ-二氰基对苯三亚甲基]及其热解产物的研究

STUDIES ON THE SYNTHESIS OF POLY (α,γ'-DICYANO-P- PHENYLENE TRIMETHYLENE) BY PHASE TRANSFER REACTION AND ITS BEHAVIOR OF PYROLYTIC PRODUCT

研究了对苯二乙腈与二氯甲烷在苄基三乙基氯化铵(BTEAC)存在下的相转移反应.合成了一种新的聚合物聚[α,γ-二氰基对苯三亚甲基](PCPTM)[Ⅰ].(PCPTM)经水解和不同温度下热处理,分别得相应水解和热解产物[Ⅱ]和[Ⅲ].对得到的聚合物进行元素分析、红外光谱和TGA分析,其中聚合物[Ⅲ]具有顺磁共振信号、较好的热稳定性和优良的半导体性质.

The phase transfer reaction of 1,4-benzene-liacetonnitrile with dichloromethane in the presence of benzyltriethylammonium chloride have been studied. Poly (α, α'-dicyano-p-pheny-lene trimethylene) (1), a new polymer, was obtained with 84% yield. The hydrolyzed product (II) was given by treating (I) with 70% sulfuric acid solution. The deep-colour resin (III1), (HII2) and (III3) were resulted from p/rolysizing of (I) under the ak condition at 250, 300 and 400℃ respectively. (III1)-(III3) exhibited excellent electronic properties, thermo-stability and strong EPR signals. Their electric resistivity at room temperature, thermal dico-mposition temperature (TGA) and corresponding g-value, line-width of EPR are 1010-107 Ω·cm, 345-408℃ and 2.00303-2.00307, 0.475-0.896 mT respectively. They are recognized as a conjugated polymer.