Polymers from multifunctional isocyanates, 3. Synthesis and polyaddition reactions of (liquid-crystalline) fully aromatic diisocyanatoesters

The regioselective reaction of aliphatic ω-isocyanatoacyl chlorides with silyl-protected hydroxy-nucleophiles was extended to aromatic isocyanatoacyl chlorides. Starting with 3- or 4-isocyanatobenzoyl chloride and 3- or 4-trimethylsiloxyphenyl isocyanate, the four isomeric isocyanatobenzoic acid isocyanatophenyl esters were synthesized in high yields. From terephthaloyl chloride and two moles of a siloxyphenyl isocyanate or from 1,4-bis(trimethylsiloxybenzene) and two moles of an isocyanatobenzoyl chloride, diesterdiisocyanates were obtained containing 3 benzene rings. The para-substituted diisocyanates show liquid-crystalline behaviour. Polyaddition reaction with various diols led to poly(esterurethane)s with a regular sequence of urethane and ester groups. The poly(urethane)s from the para-substituted diisocyanates have very high melting points (225–350°C). Liquid crystallinity could not be proven unambiguously due to the instability of the urethane linkage at these temperatures.