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ÊéÃû Polycondensation
×÷ÕßHans Kricheldorf
Ò³Êý291
³ö°æÉçspringer
ISBN 978-3-642-39428-7
Ŀ¼
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Part I History
2 Experiments Before World War I . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1 Early Formulas and Terminology . . . . . . . . . . . . . . . . . . . . . 7
2.2 First Syntheses of Polyesters . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3 Polypeptides and Polyamides . . . . . . . . . . . . . . . . . . . . . . . . 15
2.4 Various Polycondensates . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.5 Bakelite and Related Polymers. . . . . . . . . . . . . . . . . . . . . . . 18
2.6 Leo Hendrik Baekeland: Biography . . . . . . . . . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3 Wallace H. Carothers: Life and Work. . . . . . . . . . . . . . . . . . . . . 27
3.1 The Early Years . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.2 The Time at DuPont . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4 Paul J. Flory and the Classical Theory of Polycondensation. . . . . 35
4.1 Introduction and Biography . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.2 The Classical Theory of Two-dimensional
Polycondensations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.3 Three-dimensional Polycondensations
of abf (abn) Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.4 Three-dimensional Polycondensations of a3 ? b2 Monomers
and the Formation of Networks . . . . . . . . . . . . . . . . . . . . . . 42
4.5 Contribution of Other Authors . . . . . . . . . . . . . . . . . . . . . . . 45
4.6 Critical Comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5 W. H. Stockmayer and the Role of Equilibration. . . . . . . . . . . . . 51
5.1 Introduction and Biography . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.2 The Jacobson¨CStockmayer (JS) Theory . . . . . . . . . . . . . . . . . 53
vii
5.3 Flory¡¯s Contribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.4 Contributions of Other Research Groups . . . . . . . . . . . . . . . . 60
5.5 Comments on the Critical Initial Monomer
Concentration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
6 Important Polycondensates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
6.1 Nylon-6 and Other Aliphatic Polyamides. . . . . . . . . . . . . . . . 69
6.2 Aromatic Polyamides (Polyaramides) . . . . . . . . . . . . . . . . . . 73
6.3 Polyimides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
6.4 Poly(alkylene terephthalate)s . . . . . . . . . . . . . . . . . . . . . . . . 79
6.5 Polycarbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
6.6 Aromatic Polyethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
6.6.1 Poly(phenylene oxide)s . . . . . . . . . . . . . . . . . . . . . . 84
6.6.2 Poly(ether solfone)s, PES¡¯s . . . . . . . . . . . . . . . . . . . 84
6.6.3 Poly(ether ketone)s, PEK¡¯s . . . . . . . . . . . . . . . . . . . 87
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Part II New Results
7 The Role of Cyclization and a New Theory
of Polycondensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
7.1 New Theoretical Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . 95
7.2 Experimental Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
7.3 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
8 Non-Stoichiometric Polycondensations. . . . . . . . . . . . . . . . . . . . . 117
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
8.2 Class I Polycondensations . . . . . . . . . . . . . . . . . . . . . . . . . . 118
8.2.1 Polycondensations in the Melt . . . . . . . . . . . . . . . . . 118
8.2.2 Polycondensations in Solution . . . . . . . . . . . . . . . . . 121
8.2.3 Interfacial Polycondensations . . . . . . . . . . . . . . . . . . 122
8.3 Class II Polycondensations . . . . . . . . . . . . . . . . . . . . . . . . . 125
8.4 Class III Polycondensations . . . . . . . . . . . . . . . . . . . . . . . . . 125
8.5 a2 ? bn Polycondensations. . . . . . . . . . . . . . . . . . . . . . . . . . 131
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
9 Ring-Opening Polycondensation . . . . . . . . . . . . . . . . . . . . . . . . . 135
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
9.2 RO-PCs of Cyclic Anhydrides . . . . . . . . . . . . . . . . . . . . . . . 137
9.3 Tin and Silicon Containing Monomers . . . . . . . . . . . . . . . . . 139
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1442014¡ª¡ª¡¶¸ß·Ö×Ӿۺϡ·Ó¢ÎÄ°æ¸ßÇå
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