ABSTRACT
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393 II. Comblike Polymers: Helical Main Chain with Flexible Side Chains . . . . . . . . . . . . . . . . . . 394
A. Polypeptides with Covalently Attached Long Alkyl Side Chains . . . . . . . . . . . . . . . . . 394 1. Poly(γ -Alkyl-α,l-Glutamate)s (PγAG-n) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396 2. Poly(α-Alkyl-β,l-Aspartate)s (PαAA-n) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
B. Ionically Attached Long Alkyl Side Chain Polypeptides . . . . . . . . . . . . . . . . . . . . . . . . 405 1. Poly(α,l-Glutamic Acid)–Alkyltrimethylammonium Cation Complexes . . . . . . . 407 2. Poly(l-Lysine)–Alkyl Sulfate Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
III. Block Copolymers: Rod-Coil Main Chain Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409 A. Helical-Rod Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
1. Copolymers with Polypeptides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410 2. Copolymers with Polyisocyanates, Polyisocyanide, and Polycarbodiimides . . . . 416 3. Copolymers with Polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
B. Nonhelical Rod Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423 1. Copolymers with Rigid Aromatic Rod Segments . . . . . . . . . . . . . . . . . . . . . . . . . . . 423 2. Copolymers with Short Monodisperse Rod Segments . . . . . . . . . . . . . . . . . . . . . . . 431
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
I. INTRODUCTION
Copolymer systems based on blocks which behave in a coil-like fashion (including di-and triblock copolymers) have been widely studied (Chapter 9). Coil-coil multiblock systems build of incompatible coil segments have been found to exist in a wide range of microphase separated supramolecular structures, such as spheres, cylinders, double diamond (DD), double gyroid (DG), and lamella. Their phase behavior mostly results from the packing constraints imposed by the connectivity of each block
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and by the mutual repulsion of the dissimilar blocks. Phase separation and therefore the resulting stable morphology in diblock systems is greatly influenced by the total degree of polymerization (DP) (N = NA+NB), the Flory-Huggins χ parameter and the composition expressed by volume fractions fA, fB, . . ..
