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Polymer Synthesis
Ø Radical polymerization
Ø Anionic polymerization
Ø Cationic polymerization
Ø Ring-opening polymerization (ROP)
Ø Ring-opening metathesis polymerization (ROMP)
Ø Condensation polymerization
Ø Supramolecular polymerization
• Species with a highly reactive center exist where polymerization takes place
e.g. a radical, a cationic, an anionic center etc
• Initiation, propagation, and usually chain transfer and chain termination steps
exist
http://www.youtube.com/watch?v=Els5JNYfHQE
• All species (monomer, dimer, trimer etc) are approx. equally reactive and
all react with each other.
§ X is usually H or a halogen atom and X-A could be monomer (M), initiator (I),
solvent (S), or polymer (P) (in which case chain transfer can be intramolecular or
intermolecular).
Synthetic utility:
i) molecular weight control - depends on monomer / initiator ratio (linear plot vs Mn)
ii) end-group functionalization, surface functionalization, and block copolymer synthesis
CHE4250 Polymers for Nanotech 21
Polymer Synthesis
Living Anionic Polymerizations : Practical Considerations
§ The counterions that give ion-pairs with the propagating anionic centers can
influence the polymerization
Only works with large counterion at low T - prevents reaction with C=O group
• ROP of cyclic ethers (e.g. ethylene oxide, propylene oxide, THF) are used to
produce polyether diols (telechelic polyethers with OH end groups) which are
used in condensation polymerizations to form polyurethane and polyester-
based thermoplastic elastomers.
• High molecular weight poly(ethylene oxide) (PEO) and its copolymers are
used (with dissolved salts) as polymeric electrolytes in rechargeable batteries.
Olefin metathesis
• Living ROMP can be used to make monodisperse polymers and also block copolymers.
Polydispersity:
A simple statistical analysis involving the most probable (Shultz-Flory) Distribution)
based on the random nature of step growth polymerization gives:
While traditional chemistry focuses on the covalent bond, supramolecular chemistry examines the
weaker and reversible noncovalent interactions between molecules. These forces include hydrogen
bonding, metal coordination, hydrophobic forces, van der Waals forces, pi-pi interactions and
electrostatic effects.
http://en.wikipedia.org/wiki/Supramolecular_chemistry
CHE4250 Polymers for Nanotech
Supramolecular Polymers 47
Self-assembly in Nature: Viral capsids
http://www.youtube.com/watch?v=7iVm1uEIyP0
2. R. H. Grubbs, Angew. Chem. Int. Ed. 2006, 45, 3760 – 3765. Olefin-Metathesis Catalysts
for the Preparation of Molecules and Materials (Nobel Lecture)