ソジウム・メチロール・フェノレートによる塩化ホスホニトリル三量体の置換反応と置換体の重合

Chlorine substitution reactions of phosphenitrilic chloride trimer (PNCi2)3 with 2, 3 or 4-HOH2CC6HsONa and 2-NaOH2CCsHtONa were carried out i n dioxane solvent under various experimental conditions. All those reactions were completed in 40 N 200 minutes in the temperature range from 60 to 103 e C. The chemical shifts of P atom were measured by 3iP-NMR spectra of P3N3C13(2-HOH2CCGHtO)3 (1), P3N3C13(3-HOH2CC6HP)3 (2) and P3N3C14(4-HOH20c6HP)2 (3).The 3iP-NMR spectra showed that the structure of (1), (2) or (3) was non-geminai or geminal pattern respectively. Water vapor, hydrogen chloride and formaldehyde were detected by gas chromatography and plastic polymers were obtained when (1), (2), P3NgC13(4-HOH2CCgHsO)3 (4), P3N3(2-HOH20c6H O)6 (5), P3N3(3-HOH2CC6HP)6 (6) and P3N3(4-HOH2CC6HsO)6 (7) were heated in the temperature range from 150 to 250 C. On the other hand, ring cleavage reaction occurred and polymers were obtained when P3N3Cls(2-OH2CCsHsO) (8) and P3NsCh(2-OH2CCs H40)2(9) were heated in the temperature range from 150 to 200C, but no polymer was obtained with P3N3(2-OH2CC6H40)3. Those polymers were stable tpward water. lt was found from TG that the polymer obtained from (8) was more stable against thermal degradation than other poiymer.The values of resistivity of films formed when (1), (8) were heated at about 300 C for 2 miRutes was 1 N 10 10i 3 st-cm.