Ferrocene-based polymers containing azo groups in their backbone: Synthesis, electrochemical and thermal analysis.

abstract: Ferrocene-based polymers contg. azo groups in their backbone were synthesized by condensation polymn. of a cationic organometallic monomer contg. two azo dye moieties and ferrocene in the backbone as well as pendent cationic iron groups with 1,3-diaminopropane, 4,4'-thiobisbenzenethiol or bisphenol A in the presence of K2CO3. The pendent cationic cyclopentadienyl moieties were then photolytically removed from the polymers yielding neutral polyferrocene analogs. The neutral polyferrocenes had mol. wts. ranging from 8000-12,000. Thermogravimetric anal. of the cationic polymers showed two defined wt. losses, with degrdn. of the azo dye overlapped with the loss of the cyclopentadienyliron moiety at temps. between 210°-300° and degrdn of the polymer backbone at 400°-500°. The neutral polyferrocenes displayed a wt. loss assocd. with the degrdn. of the azo dye around 210°-300°. Degrdn. of the polymer backbone occurred between 400°-500°. The cationic polymers showed glass transition temps. between 126°-164°, whereas the neutral polymer displayed glass transition temps. at significantly lower temps., i.e., 85°-92°. UV-visible studies of the polymers showed they displayed a λmax similar to that of the unreacted azo dye. [on SciFinder(R)] Cited Reference: Citations: 1) Abd-El-Aziz, A; Macromolecules Containing Metal and Metal-Like Elements 2003, 1|2) Abd-El-Aziz, A; Metal-Containing Polymers, in "Ency-clopedia of Polymer Science and Technology", 3rd Edition 2002|3) Abd-El-Aziz, A; Macromol Rapid Commun 2002, 23, 995|4) Abd-El-Aziz, A; Coord Chem Rev 2003, 246, 3|5) Abd-El-Aziz, A; Macromol Chem Phys 2003, 204, 555|6) Abd-El-Aziz, A; Macromolecules 2002, 35, 8929|7) Abd-El-Aziz, A; Macromol Rapid Commun 2004, 25, 1497|8) Natansohn, A; Chem Rev 2002, 102, 4139|9) Hasegawa, M; J Appl Polym Sci 2002, 86, 17|10) Huang, K; Macromolecules 2002, 35, 8653|11) Uznanski, P; J Appl Polym Sci 2002, 86, 1456|12) Samyn, C; Macromol Rapid Commun 2000, 21, 1|13) Iftime, G; Chem Mater 2002, 14, 168|14) Tawa, K; Macromolecules 2001, 34, 8232|15) Wu, L; Macro-molecules 2001, 34, 8005|16) Nguyen, P; Chem Rev 1999, 99, 1515|17) Hudson, R; J Organomet Chem 2001, 47, 63