Sommaire: Synthetic- and natural rubber-based telechelic polyisoprenes
General introduction
Chapter I : Literature on block copolymers based on PI
Introduction
I. General strategies to synthesize block copolymers
I.1 Synthesis of well-defined linear AB diblock copolymers
I.2 Synthesis of well-defined ABA triblock copolymers
II. Synthesis of block copolymers based on polyisoprene
II.1 Using anionic polymerization.
II.1.1 Synthesis of AB diblock copolymers
II.1.2 Synthesis of ABA triblock copolymers
II.2 Using controlled/living radical polymerizations
II.2.1 Nitroxide-Mediated Radical Polymerization (NMP)
II.2.1.1 Synthesis of AB diblock copolymers
II.2.1.2 Synthesis of ABA triblock copolymers
II.2.2 Reversible Addition-Fragmentation Chain transfer Polymerization (RAFT)
II.3 Using a combination of various polymerizations
II.3.1 Synthesis of AB diblock copolymers
II.3.2 Synthesis of ABA triblock copolymers
Conclusion.
References.
Chapter II : Synthesis of block copolymers based on PI by RAFT polymerization
Introduction
I. Synthesis and characterization of polyisoprene
II. Synthesis and characterization of polyisoprene-b-poly(tertbutyl
acrylate) block
copolymers
Conclusion
Experimental section
References
Chapter III : Synthesis of natural rubber-based telechelic cis-1,4-polyisoprenes and their use to prepare block copolymers via RAFT polymerization
Introduction
I. Synthesis of α α-trithiocarbonyl-ωω-carbonyl-cis-1,4 polyisoprene
II. Synthesis of PI-b-P(t-BA) diblock copolymer
Conclusion
Experimental section
References
Chapter IV : One-pot synthesis of natural rubber-based telechelic cis-1,4polyisoprene and their use to prepare block copolymers by RAFT polymerization
Introduction
I. Functional Metathesis Degradation
II. Synthesis of P(t-BA)-b-PI-b-(P(t-BA) triblock copolymers
Conclusion
Experimental section
References
Chapter V : Thermal properties of block copolymers based on PI/P(P(t-BA) and PI/PAA
Introduction
I. Comparison between PI-macroCTA and block copolymers based on PI/P(t-BA)
II. Influence of the PI microstructure
III. Deprotection of t-BA group and thermal stability of resulting block copolymers based on PI/PAA
Conclusion
Experimental section
References
General conclusion
Extrait du mémoire synthetic- and natural rubber-based telechelic polyisoprenes
Chapter I: Literature on block copolymers based on PI
Introduction
Block copolymers are a fascinating class of materials made by covalent bonding of two or more chemically different polymeric chains (blocks) that, in most cases, are thermodynamically incompatible giving rise to a rich variety of microstructures in bulk and in solution.
Therefore, they are materials with unique chemical and physical properties: they combine the properties of individual blocks in one molecule. 1 They have attracted a great deal of attention both academically and industrially due to their wide range of potential applications2-3.
Block copolymers which contain polyisoprene (PI) as a block have found applications as nanofibers, 4 thermoplastic elastomers, 5 pressure sensitive adhesives, 6-7 and biocompatible materials. 8-9
This is due to the fact that PI is of great interest for its low glass transition temperature (T), for its double bond rich composition, for its 1,4-microstructure and because it has been classified as a biopolymer. g 10 The objective of our research work is the synthesis of AB diblock copolymers and symmetric ABA triblock copolymers based on PI block (A) and a polar poly(tert-butyl acrylate) P(t-BA) block (B) in order to get novel polymeric materials. Therefore, in this
chapter, we report on the general strategies to synthesize block copolymers that lead to well-defined linear AB and ABA block copolymers and focus on the preparation of architecturally well-defined linear AB diblock and ABA triblock copolymers based on PI.
I. General strategies to synthesize block copolymers
Various architectures of linear block copolymers such as AB diblock, ABA and ABC triblocks, (AB) multiblock are shown in Figure I-1.
The use of controlled/living polymerization techniques are the most convenient and efficient methodology to target well-defined block copolymers. In this section, the synthetic strategies based on controlled/living polymerization techniques that lead to the preparation of linear AB diblock and ABA triblock copolymers will be presented.
I.1 Synthesis of well-defined linear AB diblock copolymers
A summary of block copolymer synthesis techniques has been provided by Hillmyer and Matyjaszewski. 12 Four methods have been reported for the preparation of AB linear diblock copolymers:
A) the sequential monomer addition,
B) site-transformation technique,
C) the use of a dual initiator and,
D) by coupling two well-defined telechelic polymers.
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