BIOLOGICAL AND SYNTHETIC POLYMER NETWORKS

Selected papers from NETWORKS 86, being the 8th Polymer Networks Group Meeting held in Elsinore, Denmark, 31 August-5 September 1986.

BIOLOGICAL AND SYNTHETIC POL YMER NETWORKS

Edited by

O. KRAMER Department of Chemistry, University of Copenhagen,

Denmark

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Softcover reprint ofthe hardcover 1 st edition 1988

British Library Cataloguing in Publication Data

Biological and synthetic polymer networks. 1. Graft copolymers I. Kramer, O. 547.7 QD3g2.G7

Library of Congress Cataloging in Publication Data

Biological and synthetic polymer networks.

Bihliography: p. Includes index. 1. Polymer networks--Congresscs. 2. Biopolymers

Congresses. I. Kramer, O. (Ole) QD3R2.P67B56 198R 547.7 87-27432

ISBN-13: 978-94-010-7097-3 e-ISBN-13: 978-94-009-1343-1 DOl: 10.1007/978-94-009-1343-1

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PREFACE

Biological and Synthetic Polymer Networks contains 36 papers selected from the papers presented at NETWORKS 86, the 8th Polymer Networks Group Meeting. NETWORKS 86 was held in Elsinore, Denmark, on 31 August 5 September 1986. A total of nine invited main lectures and 68 contributed papers were presented at the meeting.

A wide range of important biological and synthetic materials consist of three-dimensional polymer networks. The properties range from very stiff structural materials to extremely flexible rubbery materials and gels. Most polymer networks are permanent networks held together by covalent bonds. Such networks are insoluble but they may swell considerably in good solvents. Polymer networks held together by ionic bonds, hydrogen bonds or so-called entanglements are of a more temporary nature. At long times they exhibit a tendency to flow, and they are soluble in good solvents. The paper by Professor Walther Burchard and his co-workers, 'Covalent, Thermoreversible and Entangled Networks: An Attempt at Comparison', serves as a general introduction to polymer networks.

The book contains both theoretical and experimental papers on the formation, characterisation and properties of polymer networks. Two topics were given special sessions at the meeting, namely Biological Networks and Swelling of Polymer Networks.

It was decided to bring scientists who study biological polymer networks together with scientists who study synthetic polymer networks. The two areas have developed different concepts and methods over the years, yet they are related enough for some of the ideas and methods of one area to be useful in the other. Synthetic polymer networks have been studied in great detail for many years and a considerable amount of basic knowledge has been obtained, both regarding the formation and characterisation of

v

VI PREFACE

polymer networks as well as the relationship between network structure and properties. The synthesis of model networks with simplified network structures has contributed considerably to this knowledge. Most biological polymer networks are found to exhibit much more complex structures than amorphous synthetic polymer networks. On the other hand, biological synthesis often leads to more perfect and regular structures than can be obtained by chemical methods.

Swelling of polymer networks is an old subject which has given rise to much confusion in the literature. However, both theory and experiment have progressed considerably during the last few years. Professor Paul .J. Flory had agreed to give a main lecture on his latest theoretical developments. This was, however, prevented by the much too early death of Professor Flory in the early autumn of 1985. The two main lectures on swelling were given by Dr Moshe Gottlieb and Dr Bruce E. Eichinger.

The book has been divided into five sections: Biological Networks. Formation of Networks, Characterisation of Polymer Networks, Swclling of Polymer Networks and Rubber Elasticity.

Finally, I should like to thank Dr S0ren Hvilsted for his valuable assistance in the editorial work.

OLE KRA\1FR

CONTENTS

Pre/Clee v

INTRODUCTORY PAPER

1. Covalent, Thermoreversible and Entangled Networks: An Attempt at Comparison 3

W. BURCHARD, R. STADLER, L. L. FREITAS, M. MOLLER. J. O"lEIS and E. MUHLEISEN (University of Freihurg, FRG)

SECTION 1: BIOLOGICAL NETWORKS

2. Structure and Rheology of Fibrin Networks 41 J. D. FERRY (University of" Wisconsin, USA)

3. Non-Gaussian Elastic Properties in Biopolymer Networks 57 J. M. GOSLINE, R. E. SHADWICK, M. E. DEMONT and M. W. DENNY (University of" British Columhia, Canada)

4. Fibrinogen and Fibrin Studied by Small-angle Neutron Scattering 79

K. MORTENSEN (RLw National Lahoratory, Denmark), R. BAUER (Veterinary and Agricultural University, Denmark) and U. LARSSON (Karolinska Institute, Sweden)

5. The Effect of Gelation on Water-Protein Interaction 87 H. TENHC, O. RIMPINEN and F. SCNDHOLM (University of Helsinki, Finland)

VII

Vlll CONTENTS

6. Structure Determination of Different Casein Components 95 A. THURN and W. BURCHARD (University of Freiburg, FRG)

7. Galactomannan-Borate Systems: A Complexation Study 113 E. PEZRON, A. RICARD, F. LAFUMA and R. AUDEBERT (Laboratoire de Physico-Chimie Macromo!eculaire, Paris, France)

8. Formation of Thermally Reversible Networks from Starch Polysaccharides 127

W. VORWERG, F. R. SCHIERBAUM, F. REUTHER and B. KETTLITZ (Central Institute of' Nutrition of the Academy of Sciences of'the GDR)

9. Insect Cuticle as a Covalently Crosslinked Protein Network 141 S. O. ANDERSEN (University of' Copenhagen, Denmark)

SECTION 2: FORMATION OF NETWORKS

10. Intramolecular Reaction and Network Formation and Properties 153

R. F. T. STEPTO (UMIST, Manchester, UK)

11. The Physics of Temporary Polymer Networks: A Comparison of Theory and Experiment 185

E. KRONER, D. CHASSAPIS and R. T AKSERMAN-KROZER (lnstitut fur Theoretische und Angewandte Physik der Universitiit Stuttgart, FRG)

12. Kinetics of Ring Formation in Polymerization Reactions 207 Lu BINGLIN (Fushin Petroleum Institute, P R China) and T. A. BAK (University of Copenhagen, Denmark)

13. Calculation of Average Network Parameters Using Combined Kinetic and Markovian Analysis . 219

D. R. MILLER (George Washington University, USA) and C. W. MAcosKo (University of Minnesota, USA)

CONTENTS IX

14. Effect of Dilution during Network Formation on Cyclization and Topological Constraints in Polyurethane Networks 233

K. DUSEK and M. ILAVSKY (Czechoslovak Academy of Sciences, C::echoslovakia)

15. 13C-NMR Analysis of Crosslin king Sites in Branched Polyesters 243

S. HVILSTED (Ris{) National Laboratory, Denmark)

16. Fluoroelastomers: Reaction Products in Early Stages of Network Formation 255

G. CIRILLO. G. CHIODINI, N. DEL FANTI, G. MOGGI (Montejiuos/CRS. Milan, Italy) and F. SEVERENI (Milan Pol.1'tec/znic, Italy)

17. A Model for Inhomogeneous Network Formation by Chain-reaction Polymerization 267

H. M. 1. BOOTS (Philips Research Laboratories. The Netherlands)

18. Sol Gel Transition Induced by Friedel-Crafts Crosslinking of Polystyrene Solutions 277

C. COLLETTE, F. LAFUMA, R. AUDEBERT and L. LEIBLER (Labo/aroire de Ph.vsico-Chimie Macromoleculaire, Paris, France)

19. Physico-chemistry of the Chromium III Interaction

Hydrolysed Polyacrylamide­in Relation to Rheological

Properties 291 C. ALLAIN and L SALOME (Laboratoire d'Hydrodynamique et Mecanique Physique. Paris, France)

20. Cured Epoxy Resins: Measurements in Dilute and Semidilute Solution 305

E. W ACHENFELD-EISELE and W. BURCHARD (University of Freiburg. FRC)

2 I. Networks as the Basis of Pre-thickening SM C 321 S. F. BUSH, 1. M. METHVEN and D. R. BLACKBURN (UMIST, Manchester, UK)

x CONTENTS

22. Special Features of Network Build-up in Curing of Poly-epoxides Based on N,N-Diglycidylaniline Derivatives 335

K. DUSEK and L. MATEJKA (Czechoslovak Academy oj' Sciences, Czechoslovakia)

23. The Influence of Vitrification on the Formation of Densely Crosslinked Networks Using Photopolymerization 345

J. G. KLOOSTERBOER and G. F. C. M. LUTEN (Philips Research Laboratories, The Netherlands)

SECTION 3: CHARACTERISATION OF POLYMER NETWORKS

24. Orientational Behaviour of Free Polymer Chains Dissolved in a Strained Network: A Deuterium Magnetic Resonance Investigation . 359

B. DaocHE, P. SOTTA (Lahoratoire de Physique des Solicies, Orsay, France), J. HERZ and A. LAPP (lnstitut Charles Sadroll. Strasbourg, France)

25. Polymer Coil Relaxation in Uniaxially Elongated Poly-(cthylethylene) Observed by Small-angle Neutron Scattering 369

K. MORTENSEN, W. BATSBERG (Riso National Laboratory, Denmark), O. KRAMER (University o( Copenhagen, Denmark) and L. J. FETTERS (Exxon Research and Engineering Co., USA)

26. The Scattering of Light by Swollen Networks 383 R. S. STEIN, V. K. SON I, H. YANG (University oj' Massa­chusetts, USA) and B. ERMAN (Bagazici University, Istanbul, Turkey)

SECTION 4: SWELLING OF POLYMER NETWORKS

27. Swelling of Polymer Networks 403 M. GOTTLIEB (Ben Gurion University, Israel)

28. Differential Swelling of Elastomers 415 B. E. EICHINGER and N. A. NEUBURGER (Universitv oj' Washington, USA)

CONTENTS

29. Phase Transition in Swollen Gels. to. Effect of the Positive Charge and its Position in the Side Chain on the Collapse and

Xl

Mechanical Behaviour of Poly(acrylamide) Networks 435 M. ILAVSKY and K. BOUCHAL (Czechoslovak Academy of Sciences, Czechoslovakia)

30. Deswelling of Gels Induced by Unidirectional Compression 449 F. HORKA Y (Hungarian Academy of Sciences, Budapest, Hungary) and M. ZRINYI (Lorand Eotvos University, Budapest, Hungary)

31. On the Temperature Dependence of Equilibrium Con-centration of Slightly Crosslinked Gels. 461

M. ZRINYI (Lorand EiitvrJs University, Budapest, Hungary) and F. HORKAY (Hungarian Academy ol Sciences, Budapest, Hungary)

32. NM R Approach to the Swelling Process of PDMS Networks and Silica-filled Siloxanes 471

J. P. COHEl"-AODAO and A. VIALLA T (Lahoratoire de S'pectro/llctrie Physique. St Martin d'Heres, France)

:n. Investigation on Polystyrene Networks Containing Pendent Poly(ethylene oxide) Chains . 483

Z. MOLFLoc, J. G. ZILLIOX, G. BEINERT, PH. CHACMONT and J. HERZ (lnstitut Charles Sadron, Strashourg, France)

SECTION 5: RUBBER ELASTICITY

34. Anisotropy of Rubber Networks Crosslinked in States of Strain 497

B. ERMAN (Bogazici University, htanhul, Turkey)

35. High-vinyl Polybutadiene Crosslinked in the Strained State to Different Degrees of Crosslinking . 509

W. BATSBERG (Riol'O National Lahoratory, Denmark), S. HVIDT (University olRoskilde, Denmark), O. KRAMER (University of Copenhagen, Denmark) and L. J. FETTERS (Exxon Research and Engineering Co., USA)

XII CONTENTS

36. A Simple Model of Random Tetrafunctional Networks with Defects . 517

A. ZIABICKI (Polish Academy of Sciencl'.s·, Warsaw, Polalld) and J. W ALASEK (Technical University, Radom, Poland)

Confrihufing Author Index 531

SuhjeC! Index 533