NOVEL POLYAROMATIC QUINONE IMINES .2. SYNTHESIS OF MODEL COMPOUNDS AND STEREOREGULAR POLY(QUINONE IMINES) FROM DISUBSTITUTED ANTHRAQUINONES

Novel poly(quinone diimines) from anthraquinones symmetrically disubst ituted with solubilizing ethyleneoxy or long chain alkoxy groups have been synthesized and characterized. The disubstituted anthraquinones 1 ,5-bis(2-methoxyethoxy)anthraquinone (EO(1)AQ), 1,5-bis(2-(2-methoxyet hoxy)ethoxy)anthraquinone (EO(2)AQ), 1,5-bis(2-(2-(2-methoxyethoxy)eth oxy)anthraquinone (EO(2)AQ, s(2-(2-2-methoxyethoxy)ethoxy)ethoxy)anthr aquinone (EO(3)AQ), 1,5-bis(octyloxy)anthraquinone (15OOAQ), 2,6-bis(o ctyloxy)anthraquinone (26OOAQ), and 1,4-bis(octyloxy)anthraquinone (14 OOAQ) were synthesized and condensed with aniline in the presence of t itanium tetrachloride and 1,4-diazabicyclo[2.2.2]octane to give -diphe nyl-1,5-bis(2-methoxyethoxy)(n)anthraquinone 9,10-diimine (DEO(n)AQ, n = 1-3), N,N-diphenyl-1,5-bis(octyloxy)anthraquinone 9,10-diimine (15D OOAQ), and N,N'-diphenyl-2,6-bis(octyloxy)anthraquinone 9,10-diimine ( 26DOOAQ), respectively, as model compounds for the polymers. The relat ive stereochemistry of these diimines was determined by H-1 NMR spectr oscopy. Polycondensation of the disubstituted anthraquinones with 4,4' -thiodianiline (SDA) gave high molecular weight (M(w) 30 000) poly(ant hraquinone diimines) and large macrocycles. Polycondensation of 1,4-ph enylenediamine (PDA) with EO(2)AQ gave high molecular weight (M(w) 14 000) polyaromatic anthraquinone diimines. PDA gave molecular weights o f M(w) 5000-23 000 for the bis(octyloxy)-substituted anthraquinones. T he molecular weights of polymerizations incorporating PDA are lowered due to steric interactions of successive repeat units and solubility c onstraints.