Reversible addition fragmentation

chain transfer
By
Dr. Dipak Pinjari
ICT, Mumbai
Outline
• Introduction
• Comparison between conventional and Controlled Radical
Polymerization
• RAFT mechanism
• RAFT outcomes
Radical Polymerization
Process involvesadding a source of radicalstoa monomer (M)
Chains are continuously initiated, propagate, anddie
RAFT
 reversible addition-fragmentation chain transfer
radical polym’n
 in (otherwise normal) radical polym’n

 use of very effective CT agent [RAFT agent]

addition fragmentation

 CCTA ~ as high as 1000

 A. and R. of similar
reactivity
RAFT Mechanism

 use [RAFT]0 >> [I]0 (like 10-fold)

 all chains with RAFT end-group  no termination
Mechanism (cont’d)

 fast and effective A-F  living-like

 MM

 all chains with RAFT end-group and living-like

 narrow MMD by that all chains grows equal rate
Kinetics
 Rp should be the same to conventional radical polym’n.
 Actually, slower. Probably due to
 radical formation by thermal initiator only
 stable adduct radical  slow fragmentation  [M]
 termination by rxn of adduct radical and other radical  [M]

 Compared to NMP and ATRP, RAFT

 is much faster
 is for much more versatile monomers
 color
RAFT agents
Fig 4.18 p112
 adduct stability (Z)

 stabilizing radical ~ reactive

 thiobenzoate > thiocarbonate > thiocarbamate > xanthate
 leaving radical stability (A)
 stable radical ~ better leaving ~ reactive
Effectiveness of RAFT Agents S S R
Strong dependence on Z substituent
Z
Less active RAFT
More active RAFT
agents provide little or
agents retard or inhibit
poor control over the
polymerization of LAMs
polymerization of MAMs

More Activated Monomers (MAMs) Less Activated Monomers (LAMs)

Me
N

switchable RAFTAgent
NH+
vinyl acetate
methacrylates N-vinylpyrrolidone
N-vinylcarbazole

styrene, acrylates, acrylamides

Effectiveness of RAFT Agents
S S R
Strong dependence on R substituent

methacrylates
methacryamides

styrene, acrylates, acrylamides

Transfer constants decrease in the series where homolytic leaving group R is Tertiary
>> secondary > primary

where -substituent on R is CN ~ Ph >> CO2R >> alkyl

where chain length of R is > 2 >> 1 (significant penultimate unit effect)

 Types of RAFT agents
Dithiobenzoates Ph
S S CH3
 Very high transfer constants
CH3
 Prone to hydrolysis
 May give retardation when used in high concentrations
Trithiocarbonates
 are readily synthesized
 high transfer constants (effective with activated monomers,e.g., acrylates,
styrene)
 give less retardation and are more hydrolytically stable(than
dithiobenzoates)
Xanthates
CN
 lower transfer constants CN
S S CH3
S S
 more effective with less activated monomers, e.g., VAc,NVP CH 3
N
 Made more active by electron‐withdrawing substituents Ph
N
CH3
Dithiocarbamates
 Activity determined by substituents on N
RAFT Polymerization
Advantages
 Simple to implement
 Low cost
 Compatible with a wide range ofmonomers
 Narrow molecular weight distribution (lowdispersity)
 Intricate control over polymer architecture& end group functionality
 Is a Reversible Deactivation Radical Polymerization(RDRP)

Disadvantages
 Need to select a RAFT agent for the specific polymerization and process conditions
 Broad molecular weight distribution (high dispersity)
 Little control over polymer architecture & end group functionality
Polymer architectures via RAFT
 RAFT Outcomes..
• It can be stopped and restarted at any time
• Polymers with controlled molecular weight, Low polydispersity
•The ability to incorporate, in a defined sequence, one or more type of
monomers in the polymer chain
•The RAFT group being retained in the final polymer, and the opportunity for
further chemical manipulation of the RAFT group, including further
polymerization or removal.
•RAFT technology also provides the ability to design polymers with highly
complex architecture