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Extra resources for Advances in Polymer Science 89
Resonances arising from 31 P are assigned to the phosphorus atoms bonded with alkyl groups (R) and trifluoroethoxy groups (F) in the three possible repeating configurations: —N=PR2~, —N=PRF- and —N = PF2-, The ratios R:F are determined from proton and phosphorus NMR, and the percentages of alkyl groups are found to agree within 5% by these two techniques. A mechanism for the reactions of the crosslinking is also proposed 168). 5 High Resolution Solid State NMR The broad Une spectra of nuclei with spin I = 1/2 in the solid state are mainly a consequence of the dominant contribution of the dipolar Hamiltonian H D (Eq.
Formation of crosslinks introduces low-frequency motions in the polymer system that affect the T2 and NOE processes but have little effect on T,. Furthermore, increasing the degree of crosslinking (up to 12% divinylbenzene) causes restriction of the molecular dynamics of the counter-ion (triethylbenzylammonium) in the polystyrene ion exchange resin phase 160). The influence of small amounts of crosslinks was examined in swollen syndiotacticrich polyimefhyl methacrylate) (PMMA) lightly crosslinked with triefhylene glycol dimethacrylate (TEDGM) and 2,2-bis[4-(2-methacryloyloxy-ethoxy)phenyl]propane (BMEPP).
8S>) Constant restrictions on segmental motion (incomplete averaging of the dipolar interactions), imposed by crosslinking, cause a T 2 plateau in the high temperature region in the spin-spin relaxation time vs temperature dependence. 5 to 2) 105) , as well as solid crosslinked cw-l,4-polybutadienes 73) exhibit a single T2 relaxation time accompanied with decreasing T2 values of plateaus as the crosslinking density increases (Fig. 16). Line shape analysis are of considerable importance in the relaxation studies of linear and crosslinked polymers, particularly of elastomers.