The characteristics of cyclic phosphazene and its applications for hard coatings

Yaguchi, A.; Mori, Shinichiro; Kitayama, Minoru; Onda, Tomohiro; Kurahashi, Akihiko; Ando, Hideyo

doi:10.1016/0040-6090(92)90880-k

Cited by 7 publications

(1 citation statement)

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“…The resulting hard film has been proposed to be of value in coatings. 34 However, we have examined the thermolysis of N 3 P 3 (O(CH 2 ) 2 OC-(vO)CMevCH 2 ) 6 and have observed preliminary evidence for the phosphazene-phosphazane rearrangement which may contribute to a decrease of the long term stability of the films by introducing the more reactive phosphazane component. The corresponding polymerization of N 3 P 3 [O(CH 2 ) 4 OC(vO)-CMevCH 2 ] 6 has been reported to yield a hard film which can be plasma etched.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

The mechanism of a phosphazene–phosphazane rearrangement

Hayes

Allen

2016

Dalton Trans.

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The phosphazene-phosphazane rearrangement of N3P3Cl5O(CH2)2OC(=O)CMe=CH2 (8) has been examined in detail using one and two dimensional NMR ((31)P, (1)H) spectroscopy and mass spectrometry. The mixed phosphazene-phosphazane [NPCl2]2[N((CH2)2OC(=O)CMe=CH2)P(O)Cl] (14), [NPCl2]2[NHP(O)Cl] (13) and a two ring assembly [NPCl2]2[NP(O{(NPCl2)2(N((CH2)2OC(=O)CMe=CH2)P(O)}] (15) have all been detected in the product mixture. The rate of the rearrangement has been measured at five temperatures by (31)P and (1)H NMR. The reaction is first order in 8 (T1/2 at 111° is 4.65 hours). The activation enthalpy is positive and the activation entropy is negative. A mechanism involving competing intra and inter molecular processes which fits the product distribution and kinetic data has been proposed. Several other methyacrylphosphazenes were examined under the same thermolysis conditions. The rearrangement was observed and the rates obtained in cases where the (CH2)2 spacer unit of the methacrylate was replaced by linear and branched propyl units. The rearrangement was not observed when the methacrylate was appended to a spirocyclic unit, the spacer unit was extended to the n-butyl group and when the methacrylate unit was replaced by a methoxy group. These results are all consistent with the proposed mechanism. This investigation resolves conflicting results previous reported for the rearrangement.

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Section: Dalton Transactions Papermentioning

confidence: 99%