TY - JOUR

T1 - Molecular conformations, hydrodynamics and optics of ladder polymers

AU - Tsvetkov, V. N.

AU - Andrianov, K. A.

AU - Makarova, N. N.

AU - Vitovskaya, M. G.

AU - Rjumtsev, E. I.

AU - Shtennikova, I. N.

PY - 1973/1

Y1 - 1973/1

N2 - Hydrodynamic (diffusion, sedimentation, viscosity), dynamo-optical and electro-optical properties of several ladder polysiloxanes with different substituents in the side groups have been investigated. In accordance with the theories of hydrodynamic properties of worm-like chains, the equilibrium rigidity of the main chain of these macromolecules was evaluated quantitatively. High equilibrium rigidity of ladder polysiloxanes is a direct consequence of the double-chain structure of their molecular chains. Values of reduced birefringence in electrical and mechanical fields in solutions of ladder polysiloxanes increase with molecular weight but tend to a limit, which is characteristic for semirigid macromolecules. Birefringence in an electrical field for solutions of all ladder polymers investigated is by two orders higher than the value of electro-optical effect in polymers with flexible chains and its sign (negative) coincides with that of flow birefringence. In a variable (sinusoidal) field in the region of high frequencies, strong frequency dependence of birefringence is characteristic for all samples. Unique electrooptical properties in constant and variable fields prove that, in contrast to polymers with flexible chains, highly organized orientational long-range order exists in ladder macromolecules, moreover, it is not only an axial order but also a polar one. The occurrence of long-range correlation in the orientation of polar groups and bonds of the molecular chain gives rise to high total moment of the macromolecule, which is responsible for its rotation in an electrical field. The direction of this dipole moment coincides with the long axis of the molecule since the Kerr effect is of the same sign as flow birefringence.

AB - Hydrodynamic (diffusion, sedimentation, viscosity), dynamo-optical and electro-optical properties of several ladder polysiloxanes with different substituents in the side groups have been investigated. In accordance with the theories of hydrodynamic properties of worm-like chains, the equilibrium rigidity of the main chain of these macromolecules was evaluated quantitatively. High equilibrium rigidity of ladder polysiloxanes is a direct consequence of the double-chain structure of their molecular chains. Values of reduced birefringence in electrical and mechanical fields in solutions of ladder polysiloxanes increase with molecular weight but tend to a limit, which is characteristic for semirigid macromolecules. Birefringence in an electrical field for solutions of all ladder polymers investigated is by two orders higher than the value of electro-optical effect in polymers with flexible chains and its sign (negative) coincides with that of flow birefringence. In a variable (sinusoidal) field in the region of high frequencies, strong frequency dependence of birefringence is characteristic for all samples. Unique electrooptical properties in constant and variable fields prove that, in contrast to polymers with flexible chains, highly organized orientational long-range order exists in ladder macromolecules, moreover, it is not only an axial order but also a polar one. The occurrence of long-range correlation in the orientation of polar groups and bonds of the molecular chain gives rise to high total moment of the macromolecule, which is responsible for its rotation in an electrical field. The direction of this dipole moment coincides with the long axis of the molecule since the Kerr effect is of the same sign as flow birefringence.

UR - http://www.scopus.com/inward/record.url?scp=0002335946&partnerID=8YFLogxK

U2 - 10.1016/0014-3057(73)90065-7

DO - 10.1016/0014-3057(73)90065-7

M3 - Article

AN - SCOPUS:0002335946

VL - 9

SP - 27

EP - 34

JO - European Polymer Journal

JF - European Polymer Journal

SN - 0014-3057

IS - 1

ER -