Interaction of Polymers with Bioactive and Corrosive Media

315 Pages·1994·30.281 MB·English

by  A.L. Iordanskii, T.E. Rudakova, G.E. Zaikov

New Concepts in Polymer Science
Interaction of Polymers with Bioactive and Corrosive Media
New Concepts in Polymer Science
Other Titles
Immobilization on Polymers
M. I. Shtilman
Radiation Chemistry of Polymers
V.S. Ivanov
Polymeric Composites
R. B. Seymour
Reactive Oligomers
S. G. Entelis, V. V. Evreinov and A.I. Kuzaev
Diffusion of Electrolytes in Polymers
G.E. Zaikov, A.L. Iordanskii and V.S. Markin
Chemical Physics of Polymer Degradation and Stabilization
N. M. Emanuel and A.L. Buchachenko
Of related interest
Journal of Adhesion Science and Technology
Editors: K.L. Mittal and W. J. van Ooij
New Polymeric Materials
Editor-in-Chief: F.E. Karasz
Journal of Biomaterials Science, Polymer Edition
Editors: C.H. Bamford, S.L. Cooper and T. Tsuruta
Composite Interfaces
Editor: H. Ishida

New Concepts in Polymer Science
Interaction of Polymers with
Bioactive and Corrosive Media
A.L. Iordanskii, T.E. Rudakova
and G.E. Zaikov
Boca Raton London New York
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First published 1994 by VSP 13V
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CIP-DATA KONINKLIJKE BIBLIOTHEEK, DEN HAAG
Iordanskii, A.L.
Interaction of polymers with bioactive and
corrosive media I A.L. Iordanskii, T.E. Rudakova, G.E.
Zaikov. -Utrecht: VSP
ISBN 90-6764-162-6 bound
NUGI 841
Subject headings: polymers.
Typeset in Lithuania by TEV. Vilnius.
Contents
Introduction xi
Preface xv
Foreword xvii
Chapter 1. Kinetic aspects of polymer interaction with components of
aggressive media 1
1.1. Introduction 1
1.2. Macrokinetic correlations of the chemical degradation processes 3
1.2.1. Internal diffusion-kinetic zone 4
1.2.2. Internal kinetic zone 7
1.2.3. External diffusion-kinetic zone 7
1.3. Degradation of polymeric materials of inhomogeneous structure 10
1.3.1. The accessibility of chemically unstable bonds in polymeric
articles 12
1.3.2. The reaction capability of chemically unstable bonds in
polymeric articles 13
1.4. Physical model of polymeric articles degradation process 15
Chapter 2. Water diffusion in polymer systems of differenth ydrophilicity 21
2.1. Introduction 21
2.2. Water sorption in hydrophobic polymers 25
2.2.1. The condition of Henry’s law fulfillment 31
2.2.2. The condition of positive deflection of the sorption
isotherm from Henry’s law 32
2.3. Water diffusion in hydrophobic polymers 35
2.3.1. Diffusion with cluster formation calculation. Formulation
and solution of the general problem 37
2.3.2. Diffusion in fluoroplasts. Partial immobilization model 38
2.3.3. Diffusional transport, complicated by continuous distribution
of sizes of water associates 39
2.4. Equilibrium water sorption in hydrophilic polymers 42
2.5. Water diffusion in hydrophilic polymers 45
2.6. Water diffusion in moderately hydrophilic polymers 51
VI Contents
Chapter 3. Transport processes in the system polymer-chemical
(biological) medium 65
3.1. Introduction 65
3.2. Diffusion features of ionized low-molecular compounds in
polymer systems 69
3.2.1. The Henderson-Planck approach 70
3.2.2. Constant field approach 70
3.3. Description of multicomponent diffusion in polymers through
thermodynamics of irreversible processes 72
3.4. Theories describing the connection of diffusion coefficients of
medium components with volume contents in polymers 75
3.5. Electrolyte state in polymer 77
3.5.1. Ions hydration 79
3.5.2. Electrolyte dissociation 82
3.5.3. Electrolyte influence on conformational behaviour of
macromolecules 83
3.5.4. Influence of macromolecular chemicals tructure on diffusion 85
3.5.5. Electrolyte action on polymer morphology 87
3.5.6. Acid sorption causing structural transition in the crystalline
phase 96
3.5.6.1. Version A 98
3.5.6.2. Version B 98
3.5.6.3. Version C 98
3.5.7. Crosslinking influence on diffusion 100
3.6. Surface phenomena complicating diffusionp rocess 103
3.6.1. External mass transfer influence on diffusion in polymers 103
3.6.2. Influence of features of polymer structural organization 106
3.6.3. Dependence of surface concentration on time 109
3.6.4. Equilibrium electrolyte sorption 113
Chapter 4. The role of diffusion processes under controlled release of
biologically active substances from polymer therapeutic
systems 125
4.1. Diffusion controlled therapeutic systems 126
4.2. The influence of solvent diffusion on the rate of release of
medicinal substance 129
4.3. Diffusion polymer systems of special purpose 136
4.3.1. Flow regulation by changing the distance between
macrochains 136
4.3.2. Permeability regulation through liquid crystal structure
formation 138
4.4. Erosive therapeutic systems 139
Contents vii
4.4.1.1. Metabolite formation 144
4.4.1.2. Capsule formation 145
4.4.1.3. Enzyme activity influence 145
Chapter 5. Diffusion and adsorption of plasma proteins — the processes,
characterizing initial stage of polymer-blood interactions 149
5.1. The role of primary adsorption and diffusion of proteins in the
general scheme of polymer-blood interaction 150
5.1.1. Diffusion-convective model 152
5.1.2. Transmission electron micrograph 152
5.1.3. Haemorheological model 152
5.2. Thermodynamic aspect of protein adsorption 153
5.3. Surface energy of polymers and plasma protein adsorption 156
5.3.1. Surface topography of polymers 158
5.4. Structural aspect of plasmic protein adsorption 159
5.5. Medium acidity influence on protein adsorption 164
5.6. The kinetic aspect of adsorption 165
5.7. The diffusive-kinetic model of protein adsorption on polymer
surface 168
Chapter 6. Polymer biodegradation: kinetics and mechanism 179
6.1. Primary reactions of the body to polymer objects 180
6.2. Medium components responsible for polymer degradation 181
6.3. Classification of resolvable polymers 182
6.3.1. Soluble polymers 183
6.3.2. Polymers decomposable via non-specific hydrolysis 184
6.3.3. Enzymatically decomposable polymers 185
6.3.3.1. General approach 185
6.3.3.2. Ways of controlling resolution rate of enzyme-splitable
polymers 190
6.3.4. Dissociating polymer-polymer complexes (PPC) 191
6.3.5. Resolvable polymer types 192
6.4. Uses and resolvability estimates 193
6.4.1. Surgical sutures 194
6.4.2. Coats for wounds and burns 197
6.4.3. Osteosynthesis pins 198
6.4.4. Resolvable polymer compositions for filling internal canals
and cavities and for use as artificial blood vessels 199
6.4.5. Coats for medical pills and tablets 200
6.4.6. Biologically active resolvable polymers 201
6.4.7. Medical adhesives 201
vili Contents
6.4.8. Biodegradable materials as medicine depots 202
6.4.9. Drug release rate from the resolvable polymer matrix 203
6.4.9.1. LMS molecules in the main chain of the polymers 204
6.4.9.2. LMS molecules attached to side chains of dissolved
polymer 204
6.4.9.3. Medicine encased in a resolvable polymer shell 205
6.4.9.4. Drug uniformly distributed in the resolvable polymer
matrix in the form of a solid solution 205
6.5. Rough estimates of resolvability and resolution times according
to model experiments 206
6.6. Kinetic regularities of drug release by biodegradable polymers 208
6.6.1. Degradation in solid polymers and solutions compared 208
6.6.2. Solid polymer degradation 210
6.6.3. Degradation of drug-containing polymers in solution 211
6.6.4. Kinetics specialities of drug-delivery polymer degradation 213
6.7. Conclusion 220
Chapter 7. Degradation and medico-biological estimation of polymers in
biological and model chemical media 233
7.1. Introduction 233
7.2. Macrokinetic features of degradation and medico-biological
estimation of fast destroyable polymers 233
7.2.1. Degradation of collagen materials in model media 234
7.2.2. Physico-chemical and medico-biological estimation of
collagen haemostatics 237
7.3. Regularities of disintegration of long lived polymers, and their
effect on a living organism 240
7.3.1. Polyethyleneterephthalate in model media and in the living
organism 241
7.3.2. Carbon composite materials’ behaviour in model media and
living organism 243
Chapter 8. Mechanical reliability of polymers in physical, chemical and
biological media 249
8.1. Introduction 249
8.2. The estimation of mechanical reliability of polymers in
aggressive media 250
8.3. Polymers in physically active aggressive media 251
8.3.1. Physical-mechanical effect 251
8.3.2. Mechanical-physical effect 260
8.4. Polymers in chemically active media 262
8.4.1. Chemomechanical effect 262