Ion-Containing Polymers. Physical Properties and Structure PDF
Preview Ion-Containing Polymers. Physical Properties and Structure
POLYMER PHYSICS Edited by R. S. STEIN Polymer Research Institute University of Massachusetts Amherst, Massachusetts Volume 1 /Introduction to Polymer Physics R. S. Stein and Joseph Powers Volume 2/Ion-Containing Polymers: Physical Properties and Structure A. Eisenberg and M. King I o n - C o n t a i n i ng P o l y m e rs PHYSICAL PROPERTIES AND STRUCTURE Polymer Physics Volume 2 A. Eisenberg and M. King DEPARTMENT OF CHEMISTRY MEAKINS CHRISTIE LABORATORIES MCGILL UNIVERSITY MCGILL UNIVERSITY MONTREAL, CANADA MONTREAL, CANADA ACADEMIC PRESS New York San Francisco London 1977 A Subsidiary of Harcourt Brace Jovanovich, Publishers COPYRIGHT © 1977, BY ACADEMIC PRESS, INC. ALL RIGHTS RESERVED. NO PART OF THIS PUBLICATION MAY BE REPRODUCED OR TRANSMITTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY INFORMATION STORAGE AND RETRIEVAL SYSTEM, WITHOUT PERMISSION IN WRITING FROM THE PUBLISHER. ACADEMIC PRESS, INC. Ill Fifth Avenue, New York, New York 10003 United Kingdom Edition published by ACADEMIC PRESS, INC. (LONDON) LTD. 24/28 Oval Road, London NW1 Library of Congress Cataloging in Publication Data Eisenberg, Adi. Ion-containing polymers. (Polymer physics treatise ; v. 2) Includes bibliographical references. 1. Polymers and polymerization. I. King, M., joint author. II. Title. III. Series. QD381.E37 547'.84 76-19491 ISBN 0-12-235050-2 PRINTED IN THE UNITED STATES OF AMERICA Preface In the past decades, the field of ion-containing polymers has experienced a very rapid growth both in terms of industrial applications and academic interest. Reflecting this high level of activity, a number of very useful reviews covering a variety of topics have appeared in the literature. A single unified treatment of the physical aspects of the subject has not yet appeared. This work attempts to fill this gap. In a field that is growing as rapidly as this one, the selection of material is obviously as much a matter of the interests and prejudices of the writers as it is the state of the field. In selecting the topics for inclusion, we were guided by the desire to include all the areas we thought would be of interest to polymer physicists, within the limitation of our own interests and avail- ability of publications on the subject. Polymers containing ions have been referred to both as "ionic polymers" and "ion-containing polymers." Both apellations are obviously correct. However, some confusion may exist, since the phrase "ionic polymers" has also been used to denote polymers synthesized by ionic polymerization mechanisms. For this reason, the phrase "ion-containing polymers" seemed preferable. Also, the latter allows the inclusion of nonionic polymers con- taining added ionic material of low molecular weight as well as some charge- transfer complexes, all of which can be classified as ion-containing. vii Acknowledgments It is a particular pleasure to acknowledge the benefit of valuable comments and suggestions from friends and colleagues who have read all or part of the manuscript, especially Drs. Z. Alexandrowicz, F. R. Eirich, H. Eisen- berg, I. Hodge, M. Mandel, E. P. Otocka, M. Pineri, T. Tanaka, Y. Wada, and K. Wissbrun. This acknowledgment obviously does not imply com- plete agreement by all these readers with all the contents, and naturally, we assume full responsibility for any remaining errors, omissions, or lack of clarity. It is also a pleasure to thank Drs. D. B. James, R. E. Wetton, C. T. Meyer, and M. Pineri for permission to present material prior to publication. Special thanks are due to Miss O. Gotts and Mrs. C. Brown for their patient typing and retyping (and retyping) of the manuscript and to Mrs. N. King for proofreading. Thanks are also due to the Graphics Department of the Weizmann Institute of Science and to Miss D. Brooks for invaluable assistance with the art work. Parts of this book were written while both of us were visitors in the Polymer Department of the Weizmann Institute of Science, and we would like to express our appreciation for their hospitality. Finally, thanks are due to the American Chemical Society, the American Institute of Physics, the Chemical Society, Huttig & Wepf Verlag, John Wiley and Sons Inc., Marcel Dekker Inc., North-Holland Publishing Company, Plenum Publishing Corporation, and the Society of Polymer Science, Japan, for peirnission to use copyrighted material. ix List of Symbols A Absorbance or length of link in stant related to second virial equivalent chain or Helm- coefficient holtz free energy or sample B( Formation constant for ion area or material dependent multiplets (i = number of constant in relation between ions in multiplet) maximum relaxation time, b Ionic sheath radius temperature and molecular b, b0 Length of segment in polymer weight or material constant model relating viscosity and molec- b Shift factor for time-tempera- T ular weight ture superposition for visco- AA\\ Absorbance perpendicular or elastic measurement for a lt parallel to direction of elon- second relaxation mechanism gation Bu Butyl a Distance between centers of BMA Butyl methacrylate charge J a Shift factor for compliance with M respect to molecular weight C Constant defined by Eq. (4), α, α Shift factor for time-tempera- Chapter IV τ τ ture superposition in visco- C,C Constants of the WLF equation l 2 elastic measurements C,, C Constants in Eq. (36), Chapter M AA Acrylic acid IV AN Acrylonitrile C Concentration of polymer p C Concentration of added salt s Β Butadiene c Concentration Β Constant relating viscosity or c Concentration of backbone f maximum relaxation time charges with molecular weight or con- c Concentration of added salt s stant relating molecular CMC Carboxymethylcellulose weight and viscosity or con- CPS Counts per second xi xii List of Symbols D Dichroic ratio or elongational f Internal energy component of t compliance or diffusion co- force of deformation efficient f' Orientation at i% elongation d Diameter of cylindrical polymer FA Formamide d Distance between scattering f(m) Function of mean charge of a sites bound counterions dBragg Bragg distance ADr - ADo Difference in RDF for salt and G Real part of (or storage) shear acid modulus DEP Diethyl phthalate G" Imaginary part of (or loss) DLS Dynamic light scattering shear modulus DMF Dimethyl formamide GA Glutamic acid DMSO Dimethyl sulfoxide GL Glycerine DOP Dioctyl phthalate G(t) Time-dependent shear modulus r DSC Differential scanning calorim- from relaxation measure- etry ments DVB Divinyl benzene Η Hookean force constant Ε Ethylene AH Enthalpy difference or line- Ε Young's modulus width in NMR Ε Real part of complex Young's ΔΗ8 Activation enthalpy modulus or apparent Young's Hv Polarization mode with verti- modulus in gel in equilibrium cally polarized incident light with swelling medium and horizontally polarized E" Imaginary part of complex analyzer Young's modulus h End-to-end distance of polymer E Young's modulus of unswollen chain Q network h* Most probable end-to-end dis- £ Activation energy tance of polymer chain act 2 2 E Electrostatic interaction energy (/i), h Mean square end-to-end dis- cl £viC8 Activation energy for viscous tance of polymer chain flow hf Mean square end-to-end dis- r e Electron charge tance of freely rotating chain Er(t) Time-dependent Young's mod- Η(τ) Distribution of relaxation times ulus from relaxation mea- surements /, I(s) Intensity of scattered radiation EA Ethyl acrylate 1(0) Intensity of incident radiation EHA Ethylhexyl acrylate Real and imaginary compo- EO Ethylene oxide nents of light scattering in EPR Electron paramagnetic reso- rheooptical tests Melt index nance F, Electrostatic force IR Infrared e / Fraction of functional chain ends or force on chain ends J Shear compliance or force constant (of Hookean J Equilibrium shear compliance t spring) or frequency or orien- J(t) Time-dependent shear com- T tation function pliance from relaxation mea- f Critical frequency surements c List of Symbols xiii Compliance function (zero m shear value) or molecular fraction mm ss κ Molecular-weight-dependent meric segment constant relating viscosity MA and ion concentration or di- late mensionless quantity in MAA X-ray scattering equation or MMA proportionality constant or MVP constant in Mark-Houwink idinium) equation MOSA Κ' Real part of dynamic strain- sulfonic acid optical coefficient or internal MQMVP field correction factor κ. Equilibrium constant N, Nt κ* Mark-Houwink constant in N Av theta solvent η κ, Static strain-optical coefficient of molecules or units or num- Dissociation constant for water ber of ion pairs in cluster k Boltzmann constant n lumber of carboxyls per scat- c κ Constant of order 1 tering site Huggins constant "o lumber of ion pairs in multi- plet L Segment length of polymer coil NMR or sample length or major axis of prolate ellipsoid or Polymer (as in PS = polysty- cylindrical polymer Ρ rene) or degree of polymeriza- Principal axis of ellipsoid Li tion ι C—C bond length = 1.54A or P Degree of polymerization be- length of chain link P tween crosslinks for Pth com- LL L-Lysine ponent Μ Metal (usually as ion) Ρ Probability of intermolecular association Μ Molecular weight M Molecular weight between ionic PPOO oorr PPrrOO c groups Μ Number average molecular <? η or charge on bead weight Number average molecular weight of unassociated poly- R Spherulite radius or distance between clusters mer Monomer molecular weight R Average cluster radius Μ Viscosity average molecular Ro Distance between multiplets ν weight Hydrodynamic radius Mw Weight average molecular R2, <R2> Mean square radius of gyration weight r Distance between centers of Weight average molecular charge or distance from scat- weight of unassociated poly- tering center or fraction of mer free counterions or end-to- xiv List of Symbols end distance of polymer chain ΤΤιι,, Spin lattice relaxation time in in rubber NMR rotating frame experi- r Distance between ith and yth ment 0 charge T,T„... Peak temperatures for α, β,... m r radius of multiplet dispersions m r2 Mean square end-to-end dis- t Time tance of chains r2 r2 in unstrained, unswollen net- u Counterion mobility 0 work 2 2 V Volume or volume of swollen r r in unconstrained state 2f 2 rubber r fr r in freely rotating configura- V Volume per carboxyl group tion Volume of multiplet 2 2 r r in θ solvent Volume of ion pair r 2e r2 r o o f° component ρ v. Volume fraction of polymer or rPP2f *f f°rr component ρ volume fraction of rubber RDF Radial distribution function v, Volume of equivalent sphere Unstrained, unswollen volume RH Relative humidity Unstrained, swollen volume S Styrene V Volume fraction of polymer in the swollen stretched state 5 Contact surface area of chain ch Volume fraction of polymer in S Surface area of multiplet m the swollen unstretched state AS Entropy of deformation of the VBTAC1 Vinyl benzyl trimethyl ammo- swollen network due to ex- nium chloride ternal strain VP Vinylpyridine AS Entropy of deformation due to 0 VSA Vinylsulfonic acid swelling AS' (=AS + AS) 0 0 W Probability distribution func- AS' AS ' for component ρ P 0 tion or interaction energy or s Scattering vector or number of work monomer units in equivalent chain link or radius of gyra- W Electrostatic energy per ion pair in cluster formation tion Work of chain stretching SAXS Small-angle X-ray scattering Electrostatic work SR Stress relaxation w Weight fraction or frequency SSA Styrene sulfonic acid (instead of ω) or resonance frequency Τ Temperature Δνν Band width in resonance experi- TJ Cluster decomposition temper- ment ature WLF Williams, Landel, and Ferry 'ζ Glass transition temperature Peak temperature, usually in tan δ versus Τ plots or tem- y Salt concentration/polymer peratures at which the WLF concentration parameters change T, T Reference temperature z Number of links in equivalent 0 re{ 7\ Spin lattice relaxation time chain List of Symbols XV ζ Valence or total concentration Damping constant or decre- of free ions ment in mechanical loss mea- ze, Excluded volume parameter surements (= π tan o) or in- due to electrostatic interac- crement or difference tion Loss or phase angle (as in tan δ = loss tangent) cf. Degree of neutralization or highest-temperature peak or Dielectric constant relaxation process in dy- Real part of complex dielectric namic studies or viscoelastic constant relaxation mechanism in- Imaginary part of complex di- volving entire chain without electric constant rupture (as opposed to / ε* Complex dielectric constant mechanism) or extension Low-frequency limit of dielec- ratio or expansion ratio tric constant ofb Strain at break ε^,^' High-frequency limit of dielec- ag Linear expansion coefficient in tric constant glassy state Δε^Δε/, Δε Relaxation strength ε — ε^ 0 y.N Expansion ratio determined by Δε2 , Δε'2 Relaxation strength of second computer simulation mechanism <χη Expansion ratio determined Δε, Excess loss due to first mech- viscometrically anism <χη ΐ Electrostatic part of ση Δε2 Excess loss of solution over (νλ)τ Ultrasound energy dissipated solvent (i.e., ε" - ε'Ή2ο) per wavelength ζ Linear charge density β Second highest temperature peak or relaxation process in η Viscosity dynamic studies or breadth [η~\ Intrinsic velocity of distribution of relaxation η' Real part of complex viscosity times or excluded volume per η" Imaginary part of complex vis- segment or thermal expan- cosity sion coefficient of swollen η* Complex viscosity stretched gel η Shear-dependent steady flow β' Peak or relaxation process near viscosity β (see above) η Steady flow viscosity 0 β0 Thermal expansion coefficient f/s Solvent viscosity of swelling medium r/ Specific viscosity sp γ Third highest peak or relaxa- tion process in dynamic Θ Scattering angle or bond angle studies or degree of counter- or "ideal" solvent ion association or constant Θ{Θ°) Primary normal stress function in Eq. 49, Chapter V (zero shear value) γ Rate of shear 6 Angle of maximum scattering m y, Extension ratio of ith coordi- nate due to both swelling and κ Rate of shear or Debye-Hiickel external strain parameter
The list of books you might like
