Aminolysis of the chlorinated poly(thionylphosphazene) [NSOCl(NPCl2)2]n (2a) with several secondary amines NHR2 (diethylamine, piperidine, and pyrrolidine) yielded various hydrolytically stable poly[(amino)thionylphosphazenes] [NSO(NR2){NP(NR2)2}2]n 6 (a, NR2 ) piperidine; b, NR2 ) pyrrolidine) in which chlorine atoms at both the phosphorus center and sulfur were replaced. In addition, treatment of 2a with different equivalents of several secondary amines (diethylamine, piperidine, and pyrrolidine), followed by addition of excess of n-butylamine, lead to a series of mixed-substituent poly[(amino)thionylphosphazenes] [NSO(NHR′){NP(NR 2)2}2]n 7 (NHR′ ) n-butylamine; a-c, NR2 ) diethylamine; d, e, NR2 ) piperidine; f, NR2 ) pyrrolidine). The new moisture stable polymers were characterized by 31 P, 13 C, and 1 H NMR spectroscopy and elemental analysis. The molecular weights of the polymers 6a,6b and 7a-7f were in the range of M h w ) 3.4 × 10 4 -1.1 × 10 5 and M h n ) 3.1 × 10 3 -5.0 × 10 4 according to GPC analysis in THF versus polystyrene standards. The thermal transition behavior was investigated by means of DSC. Glass transition temperatures (Tg's) of the poly[(amino)thionylphosphazenes] 6a,6b and 7a-7f depend on the content of secondary amine versus primary amine and were in the range of -13 to +27 °C. No melt transitions were detected.

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Poly(arylazophosphonate)s are synthesized from bifunctional diazonium salts and bifunctional phosphoric diesters by interfacial polycondensation at the interface water/organic solvent. The azo unit is formed via N-P coupling during the polycondensation reaction in satisfying yield and selectivity. Fifteen new polymers were synthesized and characterized by common methods such as 1H, 13C, and 31P NMR, FTIR, UV/visible spectroscopy, and DSC and GPC measurements. According to first laser ablation experiments as well as film forming properties and thermal and photochemical behavior, poly(arylazophosphonate)s seem to be suitable materials for ablation with XeCl excimer lasers.

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SEM image of sub micro structures of polymer APU 5 generated in experiments using a phase mask (line width: 0.3-0.5 mm, trench width: 0.3-0.5 mm, fluence: 3 J/cm 2 ).

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