Crystallization of Polymers. Volume 1, Equilibrium Concepts

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x Preface to second edition of both microscopic and macroscopic properties of crystalline polymers. Thus, the book should be helpful in understanding and solving many technological problems involving crystalline polymers. Students and investigators entering this research field for the first time should find a clear and objective perspective of the existing problems, as well as those that are reasonably well understood. For those who have been carrying out research in crystalline polymers, the problems are defined in a manner so as to indicate the directions that need to be taken to achieve resolution. It was pointed out in the preface to the first edition, that it was composed of three major portions. These three portions have now grown to three volumes. The first of these is concerned with equilibrium concepts. The second deals with the kinetics and mechanisms of crystallization. Morphology, structure and properties of the crystalline state are discussed in the third volume. There is a strong interconnection between these major subjects. The author is indebted to several generations of students and post-doctoral research associates, whose dedication, enthusiasm and love of research has sustained and contributed greatly to our research effort. It is also a pleasure to acknowledge a great debt to Mrs. Annette Franklin for her expert typing of the manuscript and preparing it in final form. The permissions granted by Acta Chimica Hungarica; Chemical Society; Colloid and Polymer Science; European Polymer Journal; John Wiley and Sons, Inc.; Journal of the American Chemical Society; Journal of Applied Polymer Science; Journal of Materials Science; Journal of Molecular Biology; Journal of Physical Chemistry; Journal of Polymer Science; Liquid Crystals; Macromolecules; Macromolecular Chemistry and Physics; Marcel Dekker, Inc.; Polymer; Polymer Engineering and Science; Polymer Journal; Pure and Applied Chemistry; Rubber Chemistry and Technology; and Springer-Verlag to reproduce material appearing in their publications is gratefully acknowledged. Thanks also to Mrs. Emily Flory, Professor C. Price and Professor J. E. Mark for the permissions that they granted. Tallahassee, Florida August, 2001 Leo Mandelkern
Preface to first edition We have been witnessing in recent years an unprecedentedly high degree of scientific activity. A natural consequence of the intensity of this endeavor is an ever-expanding scientific literature, much of which contains information of importance and interest to many diverse disciplines. However, it is a rare scientific investigator indeed who has either the time or the opportunity to digest and analyze critically the abundance we enjoy. Nowhere is this problem more acute than in the studies of the properties and behavior of macromolecular substances. Because of the somewhat belated recognition of its molecular character, this class of substances has been susceptive to quantitative investigations only for the past 30 years. During this period, however, there has developed a very rapidly increasing amount of activity and knowledge, in the realm of pure research as well as in industrial and practical applications. The problems presented have engaged the attention of individuals representing all the major scientific disciplines. In this situation it was inevitable that many subdivisions of polymer science have evolved. It appeared to the author that some of these areas could be subjected to a critical and, in some instances, a definitive analysis. Such endeavors also serve the purpose of acting as connecting links between the different specialities. At the same time they tend to underscore the more general and fundamental aspects of the scientific problems. The present volume was suggested and stimulated by the aforementioned thoughts. We shall be concerned here with the phenomena and problems associated with the participation of macromolecules in phase transitions. The term crystallization arises from the fact that ordered structures are involved in at least one of the phases. The book is composed of three major portions which, however, are of unequal length. After a deliberately brief introduction into the nature of high polymers, the equilibrium aspects of the subject are treated from the point of view of thermodynamics and statistical mechanics, with recourse to a large amount of experimental observation. The second major topic discussed is the kinetics of crystallization. The treatment is intentionally very formal and allows for the deduction xi
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Page 5 and 6: CRYSTALLIZATION OF POLYMERS SECOND
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Page 10 and 11: viii Contents 4.3 Two chemically id
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Page 17 and 18: 1 Introduction 1.1 Background Polym
Page 19 and 20: 1.2 Structure of disordered chains
Page 25 and 26: 1.3 The ordered polymer chain 9 Tab
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Page 31 and 32: 1.4 Morphological features 15 Fig.
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Page 39 and 40: References 23 5. Wilson, E. B., Jr.
Page 41 and 42: 2.1 Introduction 25 Fig. 2.1 Fusion
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2.3 Fusion of the n-alkanes and oth
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2.4 Polymer equilibrium 49 Fig. 2.1
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2.4 Polymer equilibrium 53 defined
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with ζ e being defined as 2σ eq =
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2.4 Polymer equilibrium 57 is thus
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2.4 Polymer equilibrium 59 The data
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2.4 Polymer equilibrium 61 crystall
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2.5 Nonequilibrium states 65 Fig. 2
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References 67 as do low molecular w
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References 69 56. Beech, D. R., C.
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3.2 Melting temperature 71 and ζ =
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3.2 Melting temperature 73 1.05 1.0
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3.2 Melting temperature 75 140 135
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3.2 Melting temperature 77 Fig. 3.4
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3.2 Melting temperature 79 Table 3.
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3.2 Melting temperature 81 crystall
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3.3 Crystallization from dilute sol
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3.4 Helix-coil transition 97 primar
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3.4 Helix-coil transition 99 transi
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3.4 Helix-coil transition 101 If wi
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3.5 Transformations without change
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3.6 Chemical reactions: melting and
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References 117 Fig. 3.28 Phase diag
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References 119 45. Sanchez, I. C. a
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References 121 121. Paternostre, L.
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4.2 Homogeneous melt: background 12
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4.3 Two chemically identical polyme
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4.4 Crystallization from a heteroge
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4.4 Crystallization from a heteroge
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References 139 20. Flory, P. J., Di
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5 Fusion of copolymers 5.1 Introduc
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5.2 Equilibrium theory 143 distribu
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5.2 Equilibrium theory 145 Here G
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5.2 Equilibrium theory 147 Fig. 5.1
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Therefore 5.2 Equilibrium theory 14
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5.2 Equilibrium theory 151 effect o
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5.2 Equilibrium theory 153 would be
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5.3 Nonequilibrium considerations 1
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5.4 Experimental results: random ty
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5.5 Branching 193 with 1,3-dioxolan
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5.6 Alternating copolymers 195 Mult
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5.6 Alternating copolymers 197 Fig.
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5.6 Alternating copolymers 199 Pair
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5.7 Block or ordered copolymers 201
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5.8 Copolymer-diluent mixtures 225
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References 227 are interconnected b
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References 229 57. Etlis, V. S., K.
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References 231 125. Montaudo, G., G
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References 233 193. Hamley, I. W.,
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References 235 267. Inoue, T., H. K
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6.2 Melting temperatures, heats and
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Table 6.1. Thermodynamic quantities
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acrylonitrile 593.2 5 021 94.7 8.5
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trans-octenamer 5 350.2 23 765 215.
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3-ethyl 3-methyl oxetane 334.2 6 27
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decamethylene adipate 352.7 42 677
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β-propiolactone 357 8 577 119.1 24
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caprolactam γ 7 502.2 17 949 158.8
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tetramethyl-p-silphenylene siloxane
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11 The value of H u was determined
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uu. Rijke, A. M. and S. McCoy, J. P
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Table 6.2. Thermodynamic quantities
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ethylene suberate 336.2 24 451 131.
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1 Adapted with permission from L. M
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Table 6.3. Unique values of thermod
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3,3 ′ -dimethyl thietane 286.2 5
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undecane amide 514.2 35 982 196.6 7
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new-TPI 12 >679.2 63 800 116 93.9 D
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i. Wrasidlo, W., J. Polym. Sci.: Po
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6.3 Entropy of fusion 311 regularit
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6.3 Entropy of fusion 313 Fig. 6.12
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6.3 Entropy of fusion 315 Table 6.5
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6.3 Entropy of fusion 317 disordere
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6.4 Polymorphism 319 of chains.(219
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6.4 Polymorphism 321 different crys
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6.4 Polymorphism 323 at 5 kbar. The
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6.4 Polymorphism 325 the conversion
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References 327 Fig. 6.16 Schematic
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References 329 43. Miller, R. G. J.
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References 331 114. Allen, G., C. B
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References 333 182. Russell, T. P.,
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References 335 256. Vogelsong, D. C
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7 Fusion of cross-linked polymers 7
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7.2 Theory of the melting of isotro
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7.2 Theory of the melting of isotro
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7.3 Melting temperature for random
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7.3 Melting temperature for random
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7.4 Melting temperature for axially
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7.5 Melting temperature for randoml
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7.6 Melting of network-diluent mixt
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7.6 Melting of network-diluent mixt
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References 355 if the cross-linkage
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8 Oriented crystallization and cont
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8.1 Introduction 359 disordered cha
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8.2 One-component system subject to
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8.3 Multicomponent systems subject
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8.4 In the absence of tension 389 8
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8.4 In the absence of tension 391 F
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8.4 In the absence of tension 393 o
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8.5 Contractility in the fibrous pr
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8.6 Mechanochemistry 403 The curve
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8.6 Mechanochemistry 405 Fig. 8.20
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8.6 Mechanochemistry 407 For exampl
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References 409 33. Ronca, G. and G.
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Author index Numbers in parentheses
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Author index 413 Cella, R.J., 219,
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Author index 415 Fujii, K., 256, 32
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Author index 417 Jakeways, R., 335
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Author index 419 Marchessault, R.H.
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Author index 421 Porri, L., 329, 33
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Author index 423 Stehling, F.C., 14
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Author index 425 Wittner, H., 232 W
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Subject index 427 comonomers, 152-4
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Subject index 429 poly(1,4-butylene
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Subject index 431 poly(1,4-isoprene
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Subject index 433 rubber enthalpy o
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