TY - JOUR

T1 - Structure-property relationships via complementary hydrodynamic approaches

T2 - Poly(2-(dimethylamino)ethyl methacrylate)s

AU - Perevyazko, Igor

AU - Lezov, Alexey

AU - Gubarev, Alexander S.

AU - Lebedeva, Elena

AU - Festag, Grit

AU - Guerrero-Sanchez, Carlos

AU - Tsvetkov, Nikolay

AU - Schubert, Ulrich S.

PY - 2019/11/7

Y1 - 2019/11/7

N2 - Here we present a combined analytical study of a homological series of poly(2-(dimethylamino)-ethyl methacrylate)s (DMAEMA) and their corresponding with methyl iodide quaternized versions poly[2-(methacryloyloxy) ethyl] trimethyl-ammonium iodide]s (QDMAEMA) in a wide range of molar masses (~7 to ~300kDa) and low dispersities (~1.1 to ~1.3). The polymers were studied predominantly in 0.2MNaCl in water at T=20.0°C applying mutually reinforcing's set of hydrodynamic methods, such as, viscometry, analytical ultracentrifugation, dynamic light scattering, isothermal diffusion and size exclusion chromatography. The manuscript provide compulsory discussions on the evaluation of physically sound values of the molar masses, hydrodynamic sizes and conformations of the macromolecules in solution. Special attention is paid to the investigation of ion-specific interactions and their influence on the hydrodynamic and molecular characteristics. The conformation of polymer chains in solution was validatedvia the classical scaling equations showing θ-conditions – [η]=0.055M0.47±0.04;s=0.006M0.50±0.02;D=1200M-0.50±0.02 for the initial DMAEMAs polymer chains and thermodynamically good ones for the quaternized macromolecules characterized by [η]=0.002M0.80±0.04;s=0.0133M0.45±0.02;D=1665M−0.55±0.02. The equilibrium rigidity was found to be visibly influenced by the overall electrostatic interactions and the presence of closely associated iodine ions to the quaternized polymer chains giving A=4.4nm in comparison to A=2.4nm for the initial macromolecules.

AB - Here we present a combined analytical study of a homological series of poly(2-(dimethylamino)-ethyl methacrylate)s (DMAEMA) and their corresponding with methyl iodide quaternized versions poly[2-(methacryloyloxy) ethyl] trimethyl-ammonium iodide]s (QDMAEMA) in a wide range of molar masses (~7 to ~300kDa) and low dispersities (~1.1 to ~1.3). The polymers were studied predominantly in 0.2MNaCl in water at T=20.0°C applying mutually reinforcing's set of hydrodynamic methods, such as, viscometry, analytical ultracentrifugation, dynamic light scattering, isothermal diffusion and size exclusion chromatography. The manuscript provide compulsory discussions on the evaluation of physically sound values of the molar masses, hydrodynamic sizes and conformations of the macromolecules in solution. Special attention is paid to the investigation of ion-specific interactions and their influence on the hydrodynamic and molecular characteristics. The conformation of polymer chains in solution was validatedvia the classical scaling equations showing θ-conditions – [η]=0.055M0.47±0.04;s=0.006M0.50±0.02;D=1200M-0.50±0.02 for the initial DMAEMAs polymer chains and thermodynamically good ones for the quaternized macromolecules characterized by [η]=0.002M0.80±0.04;s=0.0133M0.45±0.02;D=1665M−0.55±0.02. The equilibrium rigidity was found to be visibly influenced by the overall electrostatic interactions and the presence of closely associated iodine ions to the quaternized polymer chains giving A=4.4nm in comparison to A=2.4nm for the initial macromolecules.

KW - Analytical ultracentrifugation

KW - Cationic methacrylates

KW - Characterization

KW - Conformation

KW - Partial specific volume

KW - Polyelectrolytes

KW - Sedimentation

KW - Solution properties

KW - Viscosity

KW - POLYMERS

KW - AQUEOUS-SOLUTIONS

KW - MACROMOLECULES

KW - BEHAVIOR

KW - LIGHT

KW - POLY(N,N-DIMETHYLAMINOETHYL METHACRYLATE)

KW - CONFORMATION

KW - WEAK POLYELECTROLYTES

KW - DYNAMICS

UR - http://www.scopus.com/inward/record.url?scp=85072565392&partnerID=8YFLogxK

U2 - 10.1016/j.polymer.2019.121828

DO - 10.1016/j.polymer.2019.121828

M3 - Article

AN - SCOPUS:85072565392

VL - 182

JO - Polymer

JF - Polymer

SN - 0032-3861

M1 - 121828

ER -