Properties of polyethylene modified with phosphonate side groups. II. Dynamic mechanical behavior

The viscoelastic behavior of phosphonate derivatives of phosphonylated low-density polyethylene (LDPE) was studied by dynamic mechanical techniques. The polymers investigated contained from 0.2 to 9.1 phosphonate groups per 100 carbon atoms and included the dimethyl phosphonate derivative and two derivatives for which the phosphonate ester group was an oligomer of poly(ethylene oxide) (PEO). The temperature dependences of the storage and loss moduli of the dimethyl phosphonate derivatives were qualitatively similar to those of LDPE. At low phosphonate concentrations, the α, β, and γ dispersion regions characteristic of PE were observed, while at concentrations greater than 0.5 pendent groups per 100 carbons atoms, only the β and α relaxations could be discerned. At low degrees of substitution, the temperature of the β relaxation T_β decreased from that of PE, but above a degree of substitution of 0.1, T_β increased. This behavior was attributed to the competing influences of steric effects which tend to decrease T_β and dipolar interactions between the phosphonate groups which increase T_β. For the phosphonate containing PEO, a new dispersion region designated as the β′ relaxation was observed as a low-temperature shoulder of the β relaxation. The temperature of the β′ loss was consistent with T_g(U) of the PEO oligomers as determined by differential scanning calorimetry, and it is suggested that the β′-loss process results from the relaxation of PEO domains which constitute a discrete phase within the PE matrix.