M. Gleria

New phosphazene-based chain extenders containing allyl and epoxide groups

In this paper we present the synthesis and the characterization of cyclophosphazenes substituted with allyl groups, their transformation in epoxide-containing cyclophosphazenes and the final utilization of these compounds as chain extenders in combination with polyamides. The reaction at high temperature of Nylon-6 with epoxy-functionalized cyclophosphazenes leads to the opening of the epoxy units by the action of both amino (—NH2) and carboxylic (—COOH) end-groups of the polymer to enhance the final molecular weight of this material. The consequences of this fact on the thermal, mechanical and visco-elastic properties of treated Nylon-6 have been also evaluated and compared to those of the pristine material. Possible utilization of these cyclophosphazenes in recycling processes for degraded polyamides could be envisaged.

CYCLOPHOSPHAZENES AS VERSATILE SUBSTRATES IN POLYMER CHEMISTRY

In this article we present the synthesis of new cyclophosphazenes and their use as chain extenders, polymers compatibilizers, and monomers.

Solid State Structure of 2,2,4,4,6,6-Hexa(β-naphthyloxo)cyclophosphazatriene and Dipole Moments of Hexa(aryloxo)cyclophosphazatrienes

The crystal and molecular structure of [NP(OC10H7)2]3 was determined by X-ray analysis. The dipole moments of this compound and of the hexa(phenoxo)cyclotriphosphazatrienes of formula [NP(OC6H3XX′Y)2]3 (X = X′ = H, Y = p-Br; X = m-CH3,. X′ = H. Y = p-Cl; X = X′ = m-CH3, Y = p-Cl; X = X′ = m-CH3, Y = H; X = X′ = H, Y = p-CH(CH3)2; X = X′ = H, Y = p-C(CH3)3) were measured in benzene at 25°C. Crystals of [NP(OC10H7)2]3 are monoclinic with unit cell dimensions a = 24.870(15), b = 7.712(8), c = 27.687(14) Å, β = 115.85(7)°; space group P21/c. The structure was refined to an agreement factor of 0.09. The phosphazene ring deviates (max. deviation 17°) from planarity. and mean distances (A) and angles (°) are P-N 1.58(1). P-O 1.58(1), O-C 1.41(2); P-N-P 120(1), N-P-N 119(1), P-O-C 124(2). The conformations of the naphthyloxo groups at P(2) and P(3) are similar, and different from the group at P(1). Dipole moment analysis showed that the solid state conformation changes in the solution state. The measured value was in agreement with a symmetric conformation in which at the O-P-O plane each naphthyloxo group is rotated by ca. 40-50° from the anti-coplanar arrangement relative to this plane. The dipole moment data for the p-substituted phenoxo derivatives agree with such a conformation, but the analysis of the dipole moment values of phosphazenes having phenoxo groups bearing more than one substituent group and p-CH(CH3)2 substituent failed to do so due to the inherent limitations of the method.

Functionalization of Poly(organophosphazenes). VI. Substituent effect on the grafting reaction of maleic anhydride onto phenoxy-substituted phosphazene polymers

In this paper we describe the solution functionalization reaction of six phenoxysubstituted poly(organophosphazenes) with maleic anhydride and the effect of the phosphazene substituents on the overall grafting yield of anhydride moieties. It was found that the phosphazene polymer substituted with 4-ethylphenoxy groups is the most reactive of the whole series of exploited materials, while that bearing 4-t-butylphenoxy groups is the most inert one. This experimental reactivity trend observed in the grafting process is accounted for on the basis of both thermodynamic and steric factors.