Pendant Cyclodicarbaphosphazatriene-Containing Monomers and\nPolymers: Synthesis, Crystal Structures and Polymerization Behavior of\n[NC(NMe<sub>2</sub>)]<sub>2</sub>[NP(O-C<sub>6</sub>H<sub>4</sub>-<i>p</i>-C<sub>6</sub>H<sub>4</sub>-<i>p</i>-CHCH<sub>2</sub>)(X)], X = Cl, OCH<sub>2</sub>CF<sub>3</sub>, OC<sub>6</sub>H<sub>5</sub>,\nOC<sub>6</sub>H<sub>4</sub>-<i>m</i>-CH<sub>3</sub>, OC<sub>6</sub>H<sub>4</sub>-<i>p</i>-Br<sup>†</sup>
Vadapalli Chandrasekhar (815391)Arunachalampillai Athimoolam (2638957)Narreddula Dastagiri Reddy (2968230)Selvarajan Nagendran (1261311)Alexander Steiner (2234449)Stefano Zacchini (1431607)Raymond Butcher (2965374)
Abstract
The reaction of the dicarbaphosphazene, [NC(NMe<sub>2</sub>)]<sub>2</sub>[NPCl<sub>2</sub>] (<b>2</b>), with the sodium salt of 4-hydroxy-4‘-vinylbiphenyl\nafforded the vinyl group containing monomer [NC(NMe<sub>2</sub>)]<sub>2</sub>[NP(Cl)(O-C<sub>6</sub>H<sub>4</sub>-<i>p</i>-C<sub>6</sub>H<sub>4</sub>-<i>p</i>-CHCH<sub>2</sub>)] (<b>3</b>). Replacement of\nthe lone chlorine atom of <b>3</b> by oxygen nucleophiles gave [NC(NMe<sub>2</sub>)]<sub>2</sub>[NP(OR)(O-C<sub>6</sub>H<sub>4</sub>-<i>p</i>-C<sub>6</sub>H<sub>4</sub>-<i>p</i>-CHCH<sub>2</sub>)] [R =\nCH<sub>2</sub>CF<sub>3</sub> (<b>4</b>); C<sub>6</sub>H<sub>5</sub> (<b>5</b>); C<sub>6</sub>H<sub>4</sub>-<i>m</i>-CH<sub>3</sub> (<b>6</b>); C<sub>6</sub>H<sub>4</sub>-<i>p</i>-Br(<b>7</b>)]. The X-ray crystal structures of <b>3</b><b>−</b><b>7</b> reveal that all the\ncyclodicarbaphosphazenes have a planar N<sub>3</sub>PC<sub>2</sub> ring; the ring carbons are completely planar, while the geometry\naround phosphorus is pseudotetrahedral. The presence of weak intermolecular hydrogen bonding {C−H---X(Cl or\nBr), C−H---N, or C−H---π} interactions in <b>3</b><b>−</b><b>7</b> leads to the formation of polymeric architectures in the solid-state.\nThe monomers <b>4</b><b>−</b><b>7</b> can be polymerized by a free-radical initiator to afford the corresponding air-stable homopolymers\n<b>8</b><b>−</b><b>11</b>. These have moderate molecular weights with polydispersity indices ranging from 1.33 to 1.58. All of these\npolymers have high glass transition temperatures and have excellent thermal stability.
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