LIVING POLYMERIZATION

Presented by: Javairia Saleem

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INTRODCTION
Living polymerization is a form of chain growth
polymerization where the ability of a growing polymer
chain to terminate has been removed
 Chain termination and chain transfer reactions are absent
 The number of propagating chains (active centers) is constant
and independent of conversion
 Sequential monomer addition results in the preparation of block
copolymers.
 Polymer chains grow at a more constant rate having controlled
molar mass
INTRODUCTION
There is only one initiation and propagation continuous as long as
there is monomer
Polymerization stops only when monomers run out, adding more
monomer restart the process
CHARACTERISTICS
Key characteristics of a living polymerization is that the chain
termination and transfer reactions are essentially eliminated from the
four elementary reactions of chain-growth polymerization leaving
only initiation and (chain) propagation reactions.
 Fast rate of initiation
 Low dispersity
 Predictable molecular weight
Monomers
CLASSIFICATION

• Living anionic polymerization

• Living cationic polymerization
• Living ring-opening metathesis polymerization
• Living free radical polymerization
• Living chain-growth polycondensations
Living anionic polymerization
• Living anionic polymerization is a living polymerization technique
involving an anionic propagating species
• Polymerization continuous until the monomer is completely consumed
and until further monomer is added.
• Living anionic polymerization is a powerful method to create novel
polymer architectures and high molecular weight polymer structures
• Monomers such as styrenes, dienes, acrylates, methacrylates,
aldehydes, epoxides, acrylonitriles and cyanoacrylates readily undergo
anionic polymerization reactions
Living anionic polymerization
Living cationic polymerization

• Living cationic polymerization is a living polymerization technique

involving cationic propagating species

• Monomers for living cationic polymerization are electron-rich alkenes e.g

vinyl ethers, isobutylene, styrene and N-vinylcarbazole.

• Initiators are binary systems consisting of an electrophile and a Lewis acid

Living ring-opening metathesis
polymerization
Involve the conversion of a cyclic olefin with significant ring-strain >5
kcal/mol to a polymer that also contains double bonds
For a ROMP reaction to be considered “living”, several guidelines must
be met
1. Fast and complete initiation of the monomer
2. Degree of polymerization must be related linearly to the amount of
monomer you started with
3. The dispersity of the polymer must be < 1.5
Living ring-opening metathesis
polymerization
Living ring-opening metathesis
polymerization
Living Free Radical Polymerization
• Living free radical polymerization is a type of living
polymerization where the active polymer chain end is a free radical
Living chain-growth
polycondensations
• Monomers preferentially react with the activated polymer end
groups over reactions with other monomers
• Self-condensation between monomers occurred more frequently
due to the low propagating species concentration
• May be through catalytic transfer polycondensation mechanism
Catalytic Transfer Polycondensation
Mechanism
• Monomers do not directly react with one another and instead the
monomer will only react with the polymer end group through a
catalyst-mediated mechanism.
Applications
Living polymerizations can be used industrially for many different
applications.
• self-healing materials
• for space equipment
• to the easy design of copolymers for ion-exchange membranes in
fuel cells
• nanoscale lithography,