The reaction of the dicarbaphosphazene, [NC(NMe2)]2[NPCl2] (2), with the sodium salt of 4-hydroxy-4′-vinylbiphenyl afforded the vinyl group containing monomer [NC(NMe2)]2[NP(Cl)(O-C6H4-p -C6H4-p-CH=CH2)] (3). Replacement of the lone chlorine atom of 3 by oxygen nucleophiles gave [NC(NMe2)]2[NP(OR)(O-C6H4-p -C6H4-p-CH=CH2)] [R = CH2CF3 (4); C6H5 (5); C6H4-m-CH3 (6); C6H4-p-Br(7)]. The X-ray crystal structures of 3-7 reveal that all the cyclodicarbaphosphazenes have a planar N3PC2 ring; the ring carbons are completely planar, while the geometry around phosphorus is pseudotetrahedral. The presence of weak intermolecular hydrogen bonding {C-H---X(Cl or Br), C-H---N, or C-H---π} interactions in 3-7 leads to the formation of polymeric architectures in the solid-state. The monomers 4-7 can be polymerized by a free-radical initiator to afford the corresponding air-stable homopolymers 8-11. These have moderate molecular weights with polydispersity indices ranging from 1.33 to 1.58. All of these polymers have high glass transition temperatures and have excellent thermal stability.
Chandrasekhar V., Athimoolam A., Dastagiri Reddy N., Nagendran S., Steiner A., Zacchini S., et al. (2003). Pendant cyclodicarbaphosphazatriene-containing monomers and polymers: Synthesis, crystal structures and polymerization behavior. INORGANIC CHEMISTRY, 42(1), 51-59 [10.1021/ic025940u].
Pendant cyclodicarbaphosphazatriene-containing monomers and polymers: Synthesis, crystal structures and polymerization behavior
Zacchini S.;
2003
Abstract
The reaction of the dicarbaphosphazene, [NC(NMe2)]2[NPCl2] (2), with the sodium salt of 4-hydroxy-4′-vinylbiphenyl afforded the vinyl group containing monomer [NC(NMe2)]2[NP(Cl)(O-C6H4-p -C6H4-p-CH=CH2)] (3). Replacement of the lone chlorine atom of 3 by oxygen nucleophiles gave [NC(NMe2)]2[NP(OR)(O-C6H4-p -C6H4-p-CH=CH2)] [R = CH2CF3 (4); C6H5 (5); C6H4-m-CH3 (6); C6H4-p-Br(7)]. The X-ray crystal structures of 3-7 reveal that all the cyclodicarbaphosphazenes have a planar N3PC2 ring; the ring carbons are completely planar, while the geometry around phosphorus is pseudotetrahedral. The presence of weak intermolecular hydrogen bonding {C-H---X(Cl or Br), C-H---N, or C-H---π} interactions in 3-7 leads to the formation of polymeric architectures in the solid-state. The monomers 4-7 can be polymerized by a free-radical initiator to afford the corresponding air-stable homopolymers 8-11. These have moderate molecular weights with polydispersity indices ranging from 1.33 to 1.58. All of these polymers have high glass transition temperatures and have excellent thermal stability.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
