2950-45-0Relevant articles and documents
ALLYL-PHENOXY-CYCLOPHOSPHAZENE COMPOUND, AND PRODUCTION METHOD THEREFOR
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Paragraph 0217, (2018/06/15)
An object of the present invention is to provide a mixture of cyclophosphazenes suitably substituted with phenoxy having a polymerizable functional group, such as allyl, on the phenyl ring and a production method for the mixture. The invention relates to a mixture of cyclophosphazene compounds that each contain a plurality of constituent units linked to each other, each constituent unit being represented by formula (I): wherein R1 and R2 are identical or different and represent C1-4 alkyl or the like, the mixture containing cyclophosphazene compounds in which 3, 4, and 5 constituent units represented by formula (I) are linked, wherein the cyclophosphazene compound containing 3 linked constituent units is cyclophosphazene compound (I-A) with a specific structure, compound (I-A) includes cyclophosphazene compounds (I-A2) and (I-A3) having a specific structure, and compounds (I-A2) and (I-A3) are present in an amount of 80 wt % or more in total in cyclophosphazene compound (I-A).
Structure and conformation of the medium-sized chlorophosphazene rings
Bowers, David J.,Wright, Brian D.,Scionti, Vincenzo,Schultz, Anthony,Panzner, Matthew J.,Twum, Eric B.,Li, Lin-Lin,Katzenmeyer, Bryan C.,Thome, Benjamin S.,Rinaldi, Peter L.,Wesdemiotis, Chrys,Youngs, Wiley J.,Tessier, Claire A.
, p. 8874 - 8886 (2014/12/09)
Medium-sized cyclic oligomeric phosphazenes [PCl2N]m (where m = 5-9) that were prepared from the reaction of PCl5 and NH4Cl in refluxing chlorobenzene have been isolated by a combination of sublimation/extraction and column chromatography from the predominant products [PCl2N]3 and [PCl2N]4. The medium-sized rings [PCl2N]m have been characterized by electrospray ionization-mass spectroscopy (ESI-MS), their 31P chemical shifts have been reassigned, and their T1 relaxation times have been obtained. Crystallographic data has been recollected for [PCl 2N]5, and the crystal structures of [PCl 2N]6, and [PCl2N]8 are reported. Halogen-bonding interactions were observed in all the crystal structures of cyclic [PCl2N]m (m = 3-5, 6, 8). The crystal structures of [P(OPh)2N]7 and [P(OPh)2N]8, which are derivatives of the respective [PCl2N]m, are also reported. Comparisons of the intermolecular forces and torsion angles of [PCl2N]8 and [P(OPh)2N]8 with those of three other octameric rings are described. The comparisons show that chlorophosphazenes should not be considered prototypical, in terms of solid-state structure, because of the strong influence of halogen bonding.
Probing the mechanism of the PCl5-initiated living cationic polymerization of the phosphoranimine Cl3P=NSiMe3 using model compound chemistry
Blackstone, Vivienne,Lough, Alan J.,Murray, Martin,Manners, Ian
, p. 3658 - 3667 (2009/09/24)
New insight into the mechanism of the ambient temperature PCl5-initiatedliving cationic chain growth polycondensation of the N-silylphosphorani mine Cl3P=NSiMe3 (1) to give poly(dichlorophosphazene), [N=PCl2]n,has been provided by studies of model compound chemistry. Investigations of the reactivity of Cl- salts ofthe proposed cationic intermediates [Cl3P=N=PCl3] + ([2] +) and [Cl3PdN-PCl2dNdPCl3] + ([6]+) toward Ph3P=NSiMe3 (3a) provided evidence that under the usual polymerization conditions that involve a high monomer to initiator ratio, propagation occurs at both chain ends. However, analogous studies of near stoichiometric processes suggested that propagation is faster at one chain end, particularly when the chains are short. In addition, experiments involving [Ph3P=N=PPh3][PCl6] ([9][PCl6]) and the N-silylphosphoranimines R3P-NSiMe 3 3a (R = Ph) and 3b (R = p-CF3C6H 4),showed that the [PCl6]- anion, which is formed in the early stages of the polymerization and has hitherto been assumed to be an innocent spectator counteranion, is actually reactive under the r eaction conditions and can initiate oligomerization and polymerization. Finally, the absence of reactions between phosphoranimines 3b or 1 with the Cl- salts of the cations [Ph3P=N-PCl2=N=PPh3]+ ([10a]+), [Ph3P=N-(PCl2=N) 2= PPh3]+ ([5]+), and [Ph3P=N-(PCl 2=N) 3-PPh3]+ ([8]+) with P-Cl bonds located internally but not at the chain ends have shown that chain branching reactions are unlikely to be significant during the polymerization. These results identify key factors that complicate the living PCl5-initiated chain growth polycondensation of 1 and potentially lead to a loss of control over molecular weight and broaden the molecular weight distributions, but also indicate that the polymer formed is essentially linear rather than branched.
