Water-Soluble Synthetic Polymers: Properties and Behavior, Volume II

279 Pages·1984·25.081 MB·English

by  P. Molyneux

Water-Soluble
Synthetic Polymers:
Properties
and
Behavior
Volume II
Author
Philip Molyneux
Department of Pharmacy
Boca Raton London New York
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Library of Congress Cataloging in Publication Data
Molyneux, Philip.
Water-soluble synthetic polymers.
Bibliography: p.
Includes indexes.
1. Water-soluble polymers. I. Title.
QD382.W3M64 1983 547.7 82-22649
ISBN 0-8493-6135-4 (v. 1)
ISBN 0-8493-6136-2 (v. 2)
A Library of Congress record exists under LC control number: 82022649
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PREFACE
Water-soluble synthetic polymers are a family of materials that have been developed
commercially and studied scientifically at an accelerating pace in recent years. Partly, this
is a reflection of the increasing diversity in the applications of water-soluble polymers as a
group-in mineral-processing, water-treatment, oil-recovery and many other areas. Partly,
also, it reflects an increasing awareness of the remarkable features of water as a solvent
towards polymers and other substances, and of the need for research on simple polymers of
this type to help us understand the way in which the more complex biopolymers function
in their native aqueous environment of the living cell.
Although several monographs and reviews have appeared on individual polymers of this
type, and their applications and other technical aspects have also been discussed, this is
apparently the first book to deal with the physical chemistry of water-soluble synthetic
polymers as a group. This collective survey enables their properties and behavior to be
compared, and to be correlated with their molecular structures for predictive purposes.
However, this has made it necessary to critically re-appraise much of the earlier fundamental
work, so that current discussions of more recent work can be put on a proper basis. Thus,
of the I 800 or so references cited, the middle two-thirds relate to the twenty-year period
centered on about I 968. Nevertheless, sufficient key recent references have also been in-
cluded so that the existing "state of the art" is delineated.
To this same end, postscripts have been added to Chapters 2, 3, and 4 of Volume I, and
to Chapters I and 2 of Volume II, listing some significant work that came to light after the
main texts of these had been completed.
Clarification of the chapter format, nomenclature, deka-deci notation, notes on the tables,
and abbreviations and symbols, will be found in Appendixes I to V, placed at the end of
these volumes.
Many of the proper names used for commercial materials (polymers and others) mentioned
in the text are registered trademarks, and these are accordingly put in italics to distinguish
them from those not so-protected (e.g. common names for dyes, official names for phar-
maceuticals). Such a distinction is uncertain in several cases because of the looseness of
usage of such names, particularly in the scientific literature.
It is a pleasure to express my thanks to my colleagues on the staff of Chelsea College,
particularly those in the Library and in the Audio-Visual Service Unit, for their unfailing
help given in these increasingly difficult times.
Philip Molyneux
July 1982
THE AUTHOR
Philip Molyneux graduated with a B.Sc. (Honours Chemistry) degree from the University
of Birmingham in 1955, and obtained his Ph.D. degree in Polymer Chemistry from the
same University in 1958. After research work at Illinois Institute of Technology, Chicago,
and at the University of Keele, Staffordshire, he joined Chelsea College, University of
London, in 1963 as a Lecturer in Pharmaceutical Chemistry.
Dr. Molyneux was elected a Fellow of the Royal Institute of Chemistry (now, Royal
Society of Chemistry) of Great Britain in 1970; he is also a Chartered Chemist.
Dr. Molyneux has presented invited lectures to various international meetings, contributed
to several books, and published numerous papers on the properties and behavior of water-
soluble polymers, as well as on polymer characterization, chemical kinetics, micelle be-
havior, and adsorption. His current major research interests include the study of the inter-
actions between polymers and other solutes in aqueous solution, and the theory of permeation
through polymer films.
To my wife, Aree, for her patience and encouragement
''And a thousand thousand slimy things''
S. T. Coleridge; The Rime of the Ancient Mariner
VOLUME OUTLINES
Volume I
Chapter I
Introduction
Chapter 2
Nonionic Polymers- Polyoxides, Polyethers, and Poly(Ethylene Imine)
Chapter 3
Nonionic Polymers - The Acrylic Group
Chapter 4
Nonionic Polymers - The Vinyl Group
Appendixes
Index to Volume I
Volume II
Chapter 1
Polyelectrolytes
Chapter 2
Interactions with Small-Molecule Cosolutes
Chapter 3
Interactions Between Polymers
Chapter 4
Polymers at Interfaces
Appendixes
Index to Volume II
TABLE OF CONTENTS
Volume II
Chapter 1
Polyelectrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
A. General Aspects ........................................................... 1
B. Theoretical Aspects ........................................................ 1
I. Counterion Binding ................................................ 2
2. Viscosity Behavior. ................................................ 3
3. Ionization and Titration Behavior of Weak Polyelectrolytes ....... 5
C. Some Practical Aspects .................................................... 7
I. Nomenclature and Abbreviations for Polysalts ..................... 7
2. Basis for the Amounts and Concentrations of Polysalts ............ 7
3. Isolation and Purification .......................................... 8
II. Important Synthetic Polyelectrolytes .............................................. 8
A. Poly(Acrylic Acid) in its Partially and Fully Ionized Forms (XPA) ....... 9
I . General Features ................................................... 9
2. Solid State Properties .............................................. 9
3. Solution Behavior. ................................................. 9
a. Aqueous Solution .......................................... 9
b. Mixed Solvents ............................................ 16
B. Poly(Ethylene Imine) in its Partially and Fully Ionized Forms (PEIHY) .. 16
1. General Features .................................................. 17
2. Solution Behavior. ................................................ 18
C. Poly(Ethylene Sulfonic Acid) (PESA) and its Salts (XPES) .............. 18
I . General Features .................................................. 18
2. Preparation, Purification, Fractionation, and Analysis ............ 20
3. Solution Behavior ................................................. 20
D. Poly(Methacrylic Acid) in its Partially and Fully Ionized Forms
(XPMA) .................................................................. 24
I. General Features .................................................. 24
2. Solution Behavior ................................................. 24
a. Aqueous Solution ......................................... 24
b. Mixed Solvents .. , ....................................... ._ 30
E. Poly(Phosphoric Acid) (PPA) and its Salts (XPP) ........................ 31
1. General Features .................................................. 31
2. Preparation, Purification, and Fractionation ....................... 31
3. Handling and Storage ............................................. 32
4. Characterization and Analysis ..................................... 32
5. Solid State Properties ............................................. 32
6. Solution Behavior ................................................. 32
a. Aqueous Solution ......................................... 33
b. Mixed Solvents ............................................ 33
F. Poly(Silicic Acid) (PSiA) and its Salts (XPSi) ........................... 33
G. Poly(Styrenesulfonic Acid) (PSSA) and its Salts (XPSS) ................. 37
1. General Features .................................................. 37
2. Preparation, Purification and Fractionation ........................ 37
3. Handling and Storage ............................................. 38
4. Analysis .......................................................... 39
5. Solid State Properties ............................................. 39
6. Solution Behavior. ................................................ 39
a. Aqueous Solution ......................................... 39
b. Mixed Solvents ............................................ 45
H. Polyvinylamine (PV Am) and its Salts (PV AmHY) ....................... 45
I. General Features .................................................. 46
2. Preparation, Purification, Fractionation and Storage .............. 47
3. Analysis .......................................................... 47
4. Solution Behavior. ................................................ 47
I. Poly(2-Vinylpyridine) (P2VP), its Salts (P2VPHY), and its N-Alkyl
(Quaternary) Derivatives (P2VRPY) ...................................... 49
I. General Features .................................................. 49
2. Preparation, Purification and Fractionation ........................ 49
3. Characterization and Analysis ..................................... 49
4. Chemical Behavior. ............................................... 49
5. Solution Behavior in the Protonated Form ........................ 49
6. N-Alkyl (Quaternary) Derivatives ................................. 50
7. Spectroscopic Behavior ........................................... 50
1. Poly(4-Vinylpyridine) (P4VP), its Salts (P4VPHY), and its N-Alkyl
(Quarternary) Derivaties (P4VRPY) ...................................... 50
I . General Features .................................................. 50
2. Preparation, Purification, and Fractionation ....................... 51
3. Characterization and Analysis ..................................... 51
4. Chemical Behavior. ............................................... 51
5. Solution Behavior in the Protonated Form ........................ 51
6. N-Alkyl (Quaternary) Derivatives ................................. 51
K. Poly(Vinyl Sulfuric Acid) (PVSA), Poly(Vinyl Alcohol-co-Vinyl Sulfuric
Acid) (PV AL-VSA), and their Salts (XPV AL-VS) ....................... 52
1. General Features .................................................. 52
2. Preparation, Purification, and Fractionation ....................... 53
3. Characterization and Analysis ..................................... 53
4. Chemical Behavior. ............................................... 54
5. Solution Behavior ................................................. 54
III. Other Synthetic Polyelectrolytes ................................................. 54
A. Poly(Diallyldimethylammonium Chloride) (Poly[N ,N-Dimethyl-3,5-
Methylenepiperidinium Chloride]) ........................................ 54
B. Poly([ (Dimethy !imino) trimethylene( dimethylimino )-hexamethylene
Dibromide] (Polybrene) .................................................. 55
C. Poly(Ethylenephosphonic Acid) ["Poly(Vinylphosphonic Acid)"] ....... 55
D. Poly(Maleic Acid) ........................................................ 55
E. Poly(2-Methacryloyloxyethane-1-sulfonic Acid) .......................... 55
F. Poly(3-Methacryloyloxypropane-1-sulfonic Acid) ........................ 55
G. Poly( 4-Vinyl benzoic Acid) ............................................... 55
H. Poly(4-Vinylbenzyltrimethylammonium Salts) ............................ 58
I. Poly[3-(Vinyloxy)propane-l-sulfonic Acid] ............................... 58
J. Poly(4-Vinylphenol) [Poly(p-Hydroxystyrene)] ........................... 58
K. Poly(4-Vinylphenyl Sulfuric Acid) ....................................... 58
L. Poly(2-Vinylpiperidine) ................................................... 58
M. Poly(4-Vinylpiperidine) ................................................... 58
N. Poly(N-Vinylsuccinamidic Acid) ......................................... 59
IV. Ionic and Ionizable Synthetic Copolymers ....................................... 59
Postscript ................................................................................ 62
References ............................................................................... 62
Chapter 2
Interactions with Small-Molecule Cosolutes ........................................... 77
I. General Features of Cosolute Effects ............................................ 77
A. Introduction .............................................................. 77
B. Significance and Applications ............................................ 77
C. Division of Cosolute Effects .............................................. 79
II. Specific Effects (Cosolute Binding) .............................................. 79
A. Introduction .............................................................. 79
B. Methods for Studying Coso lute Binding .................................. 81
1. General Considerations ........................................... 81
2. Equilibrium Dialysis (ED) ....................................... 101
a. Basis of the Method ...................................... 101
b. Limitations ............................................... 102
c. Experimental Tactics ..................................... 103
d. Analysis of the Equilibrated Phases ...................... 103
e. Experimental Techniques and Equipment. ................ 104
3. Ultrafiltration (UF) ............................................... 105
4. Dynamic Dialysis (DD) .......................................... 105
5. Cosolute Partition Equilibrium (PE) .............................. 105
6. Cosolute Solubility (CS) ......................................... 106
7. Polymer Solubility (PS) .......................................... 106
8. Calorimetry (CAL) ............................................... 108
9. Gel Equilibria (GE) .............................................. 109
10. Chromatographic Methods- Gel Permeation (GPC) and Filter
Paper (FPC) ...................................................... 10 9
11. Light Scattering (LS) ............................................ 110
12. Viscometry (VI), Thermally Reversible Gelation (TRG), and Other
Rheological Techniques .......................................... 110
13. Ultracentrifuge Methods- Sedimentation Equilibrium (SE) and
Sedimentation Speed (SS) ........................................ 111
14. Electrochemical Methods ........................................ 111
a. Potentiometry (EMF) ..................................... 111
b. Polarography (POL) ...................................... 112
c. Electrical Conductivity (EC) .............................. 112
d. Electrophoresis (EPH) .................................... 112
15. Spectroscopic Methods ........................................... 113
a. General Features ......................................... 113
b. Electronic Absorption Spectra- Ultraviolet (UV) and
Visible Light (VL) Regions .............................. 113
c. Fluorescence (FL) ........................................ 114
d. Optical Rotary Dispersion (ORD) and Circular Dichroism
(CD) ...................................................... 114