chapter  4
72 Pages

4

I. Introduction ................................................................ 162 II. Theoretical Aspects of the Dynamics of Micelles

of Block Copolymers................................................... 166 A. AWK Theory for the Dynamics of Surfactant

Micelles and Main Conclusions Drawn from Results for Surfactant Solutions ........................ 167

B. Analytical Treatments of the Dynamics of Block Copolymer Micelles................................... 170

C. Dynamic Monte Carlo Simulations.................... 172 III. Dynamics of Block Copolymer Micelles: Historical

Aspects, Methods of Investigation, and General Observations ............................................................... 175

IV. Dynamics of Micelles of Poly(Ethylene Oxide)- Poly(Propylene Oxide)-Poly(Ethylene Oxide) Block Copolymers in Aqueous Solution.................... 177 A. Qualitative Features ........................................... 177 B. Quantitative Features......................................... 185

1. Exchange Rate Constants............................. 185

2. Micelle Formation/Breakdown...................... 190 C. Conclusions .......................................................... 192

V. Dynamics of Micelles of Copolymers Other than EON(EO)PON(PO)EON(EO) in Aqueous Solution and in Organic Solvent .............................................. 192 A. General Considerations....................................... 192 B. Dynamics of Copolymer Micelles in Aqueous

and Hydro-Organic Solution............................... 193 C. Dynamics of Copolymer Micelles in

Organic Solution.................................................. 201 VI. Dynamics of Exchange of Solubilizates in Micellar

Solutions of Block Copolymers.................................. 209 A. Rate of Release (Exit) of Solubilizates from

Block Copolymer Micelles................................... 211 B. Rate of Entry of Solubilizates into Block

Copolymer Micelles ............................................. 214 VII. Dynamics in Aqueous Solution of Associative

Polymers...................................................................... 216 A. Telechelic Polymers ............................................. 216 B. Comblike Polymers.............................................. 218

VIII. Dynamics of Miscellaneous Processes Occurring in Block Copolymers Systems ................................... 220

IX. General Conclusions................................................... 222 References ........................................................................... 224

I. INTRODUCTION

Amphiphilic copolymers are obtained by the copolymerization of two (or more) monomers. They can be synthesized with an enormous variety of structures of the block type, graft type, comb type, alternating type, or random type.1 Within each type of structure, the chemical diversity of the monomers that can be used to generate copolymers is very large and restricted only by the ability of the polymer chemist to synthesize the monomers and perform the polymerization required for obtaining the desired copolymer with the desired structure. This diversity, together with the possible changes of composition, molecular weight, and architecture of the copolymers, underlines the large number of parameters that

are going to determine the equilibrium as well as the dynamic properties of amphiphilic copolymers in solution.