Ionic conductivity of complexes of novel multiarmed polymers with phosphazene core and LiClO4

✍ Scribed by Kenzo Inoue; Hidehito Miyamoto; Tomoyuki Itaya

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 217 KB
• Volume: 35
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(19970715)35:9<1839::aid-pola25>3.0.co;2-5

✦ Synopsis

Novel multiarmed polymers with ethylene oxide units, [({CH 2 CH 2 O) n {: 7, n Å 3; 8, n Å 7.2; 9, n Å 11.8, and 12, n Å 11.8) were prepared from the reaction of polyethylene glycol monomethyl ethers with acid chlorides of hexakis(3,5-dicarboxyphenoxy)-( 6) and hexakis(4-carboxyphenoxy)cyclotriphosphazenes ( 11) and conductivities of their Li / salt complexes were investigated. The glass transition temperatures of the salt-free polymers are in the temperature range 059 to 054ЊC, indicative of a high degree of reorientational mobility of the arms. When LiClO 4 was added to the multiarmed polymers, the T g values raised monotonically. The extent of T g elevation was affected by the length of arms and the number of oxygen atoms around cyclotriphosphazene core and increased in the order 7 ú 8 ú 12 ú 9. The conductivities increased in the order 9 ú 8 Å 12 ú 7 and the maximum conductivities of 4.0 1 10 05 S/cm at 30ЊC and 6.0 1 10 04 S/cm at 90ЊC have been achieved for the 9-Li / complex with Li / /O Å 0.03. Interestingly, the conductivity of 9-Li / complexes at constant reduced temperatures increased in the whole concentrations of LiClO 4 examined (Li / /O Å 0.01-0.2), although the degree of increase in conductivity above Li / /O Å 0.06 became small. From the behaviors of T g and the conductivity of multiarmed polymer-LiClO 4 complexes, it appears that the conductivity is governed by relative concentrations of interand intramolecular complexes in the polymer matrix. The influence of structural change of the comb-shaped to multiarmed polymers on the conductivity is described. ᭧ 1997