纸质出版日期:1995-8-20
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用交流复阻抗谱和动态粘弹谱等对交替马来酸酐共聚物多缩乙二醇酯衍生物及其LiClO4盐复合物进行了研究.结果表明,在Li/EO=0.07—0.042范围内,从173K到373K,本聚合物一高氯酸锂复合体系的动态粘弹谱存在着两个明显的转变,其中β转变归属于PEO的侧链玻璃化转变,转变温度随LiClO4盐浓度的增加而增加。α转变归属于主链玻璃化转变,在Li/EO=0.028时有极大值。盐浓度与电导率的关系与通常不一样,在所研究盐浓度范围内观察到两个峰,其一在Li/EO<0.014,另一峰在Li/EO=0.028.电导率与温度的依赖关系不符合Arrhenius行为;以lgσ对1/T-T0作图,用侧链玻璃化转变温度Tβ作T0时,呈典型的VTF行为。该体系室温电导率最高可达6×10-6s/cm.
The amorphous comblike polymers based on methylvinyl ether/maleic anhydride alternating copolymer backbone and on oligo-oxyethylene side chains were synthesized according to our previous work.The dynamic mechanical properties of the polymers and their LiClO4 complexes were investigated by means of DDV-II-EA type viscoelastic spectrometry.The results show that the polymers and their LiClO4 complexes possess two type of transition in.the temperature range from 173K to 373K.β-transition of the polymer is assigned to PEO side chains.The temperatu-re of β-transition increase with increasing LIClO4 amount added.a-transition of the polymer is assigned to the polymer main chains.As for the a-transition temperatu-re.when the salt content increases there is a maximum at the ratio of Li/EO being 028.The relation between LiClO4 amount added and conductivity is rather comp-lex.It shows more than one peaks,one is located in the range of ratio of Li/EO less than.014.another one is located at the ratio of Li/EO =.028.The tempera-ture dependence of ionic conductivity was studied Data indicate the Arrhenius re-lationship is not held.But the plot of lgσ against 1/(T—To) shows the unusual dual VTF behavior when using side chains glass transition temperature as To.This is attributed to the a-transition of the polymer main chains.
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