長鎖アルキルリン酸エステルの熱分解
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概要
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Assessment was made of the thermal stability of long-chain alkyl phosphate by thermal analysis (TG/DTA/DSC). Several monoalkyl phosphates (C<SUB>n</SUB>-MAP) differing in chain length (C<SUB>12</SUB>, C<SUB>14</SUB>, C<SUB>16</SUB>) showed essentially the same thermal stability. The decomposition temperature of didodecyl phosphate (C<SUB>12</SUB>-DAP) was 257.8°C [40-50°C higher than that of monododecyl phosphate (C<SUB>12</SUB>-MAP)]. C<SUB>12</SUB>-MAP·2 Na salt was thermally more stable than C<SUB>12</SUB>-MAP, but C<SUB>12</SUB>-MAP·Na salt was less stable than this.<BR>Gas chromatographic analysis of the decomposition gas indicated dodecene to be mainly formed from C<SUB>12</SUB>-MAP, whereas 1-dodecanol from C<SUB>12</SUB>-MAP·Na salt and C<SUB>12</SUB>-MAP·2 Na salt.<BR><SUP>31</SUP>P-NMR analysis of C<SUB>12</SUB>-MAP decomposition mixtures revealed that the disproportionation of C<SUB>12</SUB>-MAP to phosphoric acid (PA) and C<SUB>12</SUB>-DAP and condensed phosphate formation fromC<SUB>12</SUB>-MAP were competetive with the elimination of olefin from C<SUB>12</SUB>-MAP.<BR>The elimination of olefins from monoalkyl pyrophosphate [Py- (1.0)] and dialkyl pyrophosphate [Py- (1, 1)] besides from C<SUB>12</SUB>-MAP thus must be taken into consideration for assessement of the thermostability of long-chain alkyl phoshates. The formation of [PA+ Py- (0, 0)] from [MAP+DAP +Py- (1, 0) +Py- (1, 1)] appears to be a zero order reaction with an activation energy of 26.2kcal/mol.
- 社団法人 日本油化学会の論文