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The reaction of a mixture of [NPCl2]n and Cs2CO3 first with (R)-(+)-1,1‘-binaphthyl-2,2‘-diol (HO−C10H6−C10H6−OH) (binaphthol) and subsequently with phenol (HO−C6H5) in refluxing 1,4-dioxane gave the series of the optically active random copolymers {[NP(O2C20H12)]x[NP(OC6H5)2]1-x}n (2). Absolute molecular weight distributions and radius of gyration have been determined by size exclusion chromatography, using simultaneously multiangle light scattering and differential refractive index detectors. The dependence of the dimensions of the polymers on the molecular weight through the corresponding scaling laws is studied. In addition, a stereochemical study of homopolymers [NP(O2C20H12)]n 1 and copolymers 2 based on the CD exciton chirality method is also included. The reaction of the partially substituted polymer [NP(R−O2C20H12)0.4(Cl2)0.6]n with the stoichiometric amount of racemic binaphthol, or with a large excess of the latter, in the presence of Cs2CO3 gave the same polymer [NP(R−O2C20H12)0.4(rac-O2C20H12)0.4]n [(−)-3] irrespective of the amount of racemic binaphthol used, showing no enantiomeric induction by the R−binaphthoxy units already present in the polymer.

The polymer [NPCl2]n reacts with the functionalized biphenols bis(2-hydroxy-5-chlorophenyl)methane [(HOC6H3Cl)2CH2], bis(2-hydroxyphenyl) ketone [(HOC6H4)2CO], and [racemic(±)]-, [R(+)]-, or [S(−)]-1,1‘-binaphthyl-2-ol [(HOC10H6C10H6OH)] (binaphthol), in THF, or 1,4-dioxane in the presence of K2CO3 or Cs2CO3 to give respectively the spirocyclic phosphazene homopolymers [NP(O2C13H8Cl2)]n (1), [NP(O3C13H8)]n (2), (±)-[NP(O2C20H12)]n (5), (−)-[NP(O2C20H12)]n [(−)-5b], and (+)-[NP(O2C20H12)]n [(+)-5b], some of them also obtained as blends with poly(tetrahydrofuran). The reaction of [NPCl2]n first with (HOC6H3Cl)2CH2 or (HOC6H4)2CO and subsequently with 2,2‘-biphenol ((HO)C6H4C6H4(OH)) in THF and in the presence of K2CO3 gave the random mixed copolymers [NP(O2C12H8)0.6(O2C13H8Cl2)0.4]n (3) and [NP(O2C12H8)0.6(O3C13H8)0.4]n (4). For comparison with the polymers, the two cyclic enantiomers (+)-[N3P3(O2C20H12)3] [(+)-6] and (−)-[N3P3(O2C20H12)3] [(−)-6] have been prepared from [N3P3Cl6] and [S(−)]- or [R(+)]-binaphthol, respectively, in acetone in the presence of Cs2CO3.

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