The equilibrium and kinetic rigidity of additive poly(trimethylsilyltricyclononenes) with one and two Si(CH 3 ) 3 groups in monomer unit

The homologous series of additive poly[3-(trimethylsilyl)tricyclononene-7] with two heminal substituents Si(CH 3 ) 3 in the side cycle of the monomer unit is studied for the first time via the methods of viscometry and static and dynamic light scattering in the range of molecular masses of (29–770) × 10 3 . The scaling ratios for the intrinsic viscosity and the coefficient of translational diffusion of macromolecules in toluene at 298 K are obtained, and the equilibrium rigidity of the polymer chain is determined. The hydrodynamic and conformation properties of the polymer are compared to an analog with only one Si(CH 3 ) 3 substituent in the monomer unit. It is found that the introduction of the second side substituent in the heminal position increases the equilibrium rigidity of the additive poly[3-(trimethylsilyl)tricyclononene-7] by 1.4 times and has a far stronger effect on the kinetic rigidity of the polymer. With the use of the 1 Н NMR relaxation method, it is shown that the mobility of side groups of the polymer with two substituents decreases significantly and the correlation times of hydrogen atoms of Si(CH 3 ) 3 groups exceed some 20 times the corresponding values for the analog with one Si(CH 3 ) 3 group in the monomer unit cycle.