After recalling the basics of chain polymerization methods, the different synthetic strategies existing today will be systematically studied (anionic, cationic, standard radical, controlled radical and coordinative polymerization methods). The scope and limitations of each method will be systematically discussed. Mechanistic and kinetic features will be then studied for each polymerization method. Special emphasis will be finally put on the control of macromolecular architectures.
Part B " Polymers in solution ":
After defining the characteristic features of polymer in solution, the Flory and Huggins' thermodynamic theory of polymer solutions will be studied. Afterwards, the Flory and Kringbaum's theory will be developed in order to describe the thermodynamics of very diluted polymer solution. The out of equilibrium behaviour, and more precisely the hydrodynamic properties, will be finally addressed. All these topics will not be necessarily covered each year.
At the end of this learning unit, the student is able to : | |
| 1 | This course aims for providing a profound understanding of chain polymerization methods as well as physico-chemical properties of polymers in solutions. The course is divided into two parts covering these two features. At this end of the course, the students are expected to deeply understand and explain the following items
Part A" Chain polymerization methods " :
Part B " Polymers in solution ": |
The contribution of this Teaching Unit to the development and command of the skills and learning outcomes of the programme(s) can be accessed at the end of this sheet, in the section entitled “Programmes/courses offering this Teaching Unit”.
1. Introduction 1.1 Chain polymerizations 1.2 Living and controlled chain polymerizations 2. Anionic polymerization 2.1 General features 2.2 Initiating systems 2.3 Mechanistic features 2.4 Examples of macromolecular architectures 2.5 Special anionic polymerization methods (group transfer polymerization, metal-free anionic polymerization, ligated anionic polymerization) 3. Cationic polymerization 3.1 General features 3.2 Initiating systems 3.3 Mechanistic features 3.4 Cationic polymerization of heterocycles 3.5 Factors allowing a living character 3.6 Examples of macromolecular architectures 4. Classical radical polymerization 4.1 Mechanistic and kinetic features 4.2 Control of molar mass (" dead-end " method) 4.3 Control of end-groups (telomerization) 4.4 The " Iniferter " method 4.5 Technology of radical polymerization 5. Controlled radical polymerization 5.1 General features 5.2 Control by nitroxides radicals (NMP) 5.3 Control by atom transfer (ATRP) 5.4 Control by reversible chain transfer (RAFT) 5.5 Control by organo-tellurium (TERP) 6. Coordinative polymerization 6.1 Ziegler-Natta catalysts 6.2 Phillips catalysts 6.3 Metallocene catalysts and tacticity control 6.4 Ring-opening metathesis polymerization 6.5 Coordinative ring-opening polymerization of aliphatic esters
Part B " Polymers in solution "
7. Solubilisation and characteristic features of polymers in solution 7.1 Solubilisation without degradation 7.2 Definitions of the physico-chemical concepts of interest 7.3 Thermodynamic concepts (free energy of mixing, ') 8. Flory and Huggins thermodynamic theory of polymer solutions 8.1 Regular solutions 8.2 Determination of the free energy of mixing 8.3 Limitations 8.4 Application to miscibility and phase separation concepts (phase diagram) 9. Flory and Krigbaum thermodynamic theory of diluted polymer solutions 9.1 The concept of excluded volume 9.2 Thermodynamic calculations 9.3 Application to membrane osmometry and tonometry 9.4 Application to light scattering 10. Out of equilibrium polymer solutions (hydrodynamic properties) 10.1 Viscosimetry 10.2 Size exclusion chromatography Methods: Lectures eventually completed by invited seminars and/or seminars prepared by the students themselves.
