Syllabus

UNIT I (Chain Polymerization)

Free radical polymerization, Role of inihibitors and
retarders, Controlled radical polymerization - Iniferters
- Atom transfer radical polymerization (ATRP) Nitroxy
radical mediated (NMP) polymerization - Reversible
addition-fragmentation chain transfer (RAFT)
polymerization. Anionic and cationic polymerizations
Living polymerization, Ring opening polymerization,
Co-ordination polymerization, Zieglar Natta catalysts,
Single site catalysts, Copolymerization, Kinetics of
polymerization and copolymerization.
Type of polymerization.
Polymerization
polymerization
Monomer Polymer

Monomer Polymer

H2C CH2 addition CH2CH2

H2C CHCl addition

CH2CH
Cl
O ring-opening
H2C CH2 CH2CH2O

condensation
HOCH2CH2OH CH2CH2O
-H2O

O
condensation
HO CO2H O C
-H2O
Type of polymerization.
Classified by polymerization mechanism:
(1) step-reaction or step-growth polymerization
(2) chain-reaction or chain-growth polymerization
(3) ring-opening polymerization (step- or chain-growth)
 CHAIN POLYMERIZATION
Free Radical Polymerization
• Free radical are independently-existing species that have
unpaired electron. Normally they are highly reactive with
short life time.
• Free radical polymerization’s are chain polymerization’s in
which each polymer molecules grows by addition of
monomer to a terminal free-radical reactive site known as
active center.
• After each addition the free radical is transferred to the
chain end.
• Chain polymerization is characterized by three distinct
stages, Initiation, propagation and termination.
 INITIATION
• This stage is a two steps stage
• 1. The formation of free radicals from an initiator.
• 2. The addition of one of these free radicals to a
monomer molecules.
• Free radical can be formed by two principal
• 1. Homolytic scission (homolysis) or breakage of a
single bond.
• 2. Single electron transferred to or from an ion or
molecule (redox reactions)
• Homolytic can be achieved by heat (thermolysis) or by
light such as U.V. (photolysis).
Example
O O O
 -C-O-O-C- 2 -C-O

Benzoly peroxide Benzolyooxy radicals

 (CH ) C-N = N- C (CH3)2 2(CH3)2C + N2

3 2

 CN CN CN
Azobisisobutyronitril 2-Cyanopropyl radicals
• Sometimes the radicals undergo further breakdown (-
scissions) such as
 O O
 -C-O + C = O 

(CH3)2 - C-O CH3 + (CH3)2-C = O
 CH3 Methyl acetone
 radical
 Promoters : Inducing initiation at lower temperature.

O O
Ph C O O C Ph + Ph N(CH3)2

CH3 O
Ph N O C Ph + Ph CO2
CH3

CH3 O
O
Ph N O C Ph Ph N(CH3)2 + Ph C O
CH3

Half-life of benzoyloxy radical : 30 min at 100℃

Half-life of isobutyronitrile radical : 1.3 hours at 80℃.
Cage effect : confining effect of solvent molecules.
 Azo Compounds

Side reaction : Cage effect.

Cage
  effect : confining effect of solvent molecules
Tetramethylsuccinonitrile

Ketenimine                
 PHOTOLYSIS

• Photolysis is the second principle of free

radical formation.
• The advantage of this method is that the
formation of free radicals begins at the
instant of exposure and ceases as soon as
the light source is removed.
 Photoinitiator

A. Peroxide and Azo compound.

 
Photolysis and thermalysis.

B. Photolabile initiator.
 Redox Initiators

  A. One electron transfer reaction

 
a. Making free radical by one electron transfer
by redox reaction.
  b. Low-temperature reaction.
 c. Emulsion polymerization.
                                                                                                                    
   B. Example of redox system
 REDOX REACTION
• Redox reaction defined as the generation of free radicals
by electron transfer and it is use when polymerization
performed at low temperature.
• Example
 CH3 CH3

 -
-C-O-OH + Fe2+` -C-O + OH + Fe3+
 CH3 CH3
 Cumyl Ferrous Cumyloyloxy
 hydroperoxide ion radical
 O O O O O O
O-S-O-O-S-O + HO-S-O O-S-O + O-S-O + OH-S-O
 O O O O
Presulphate Bisulphate Sulphate Sulphate Bisulphate
 ion ion ion radical radical
• An active center is created when a free radical (Ro) which
is generated from an initiator attacks the -bond of the
monomer molecules. 

R + CH2 = CH R-CH2-CH or R-CH - CH2

X X X
This is more This is more
likely stable
Sometime free radical react with each other such as:
O O O
2 -C-O -C-O- +C=O
 
OR
 
2
 Thermal Polymerization

A. Polymerization without initiators.

 
a. Dimer formation by Diels-Alder reaction.

The Diels-Alder reaction is an

organic chemical reaction (specifically, a cycloaddition)
2CH2 CHPh between a conjugated diene and a substituted alkene,
commonly termed the dienophile, to form a substituted
cyclohexene system.
H Otto Paul Hermann Diels and Kurt Alder first docu-
Ph mented the novel reaction in 1928 for which they were
awarded the Nobel Prize in Chemistry in 1950 for their

10 work on the eponymous reaction.

b. Radical formation from dimer.

·
10 + CH2 CHPh ·
CH3CHPh +

Ph

11 12
 PROPAGATION
• The addition of monomer molecules to the active center to grow the
polymer chain. 
• There are two modes of chain propagation
1. Head to Tail
R-CH2-CH + CH2=CH R-CH2-CH-CH2-CH
X X X X
2. Head to Head
R-CH2-CH + CH2=CH R-CH2-CH-CH-CH2
X X X X
Again mode (1) are more dominant.
Therefore polymer structure are like
 -----CH -CH-CH -CH-CH -CH-CH -CH------
2 2 2 2
X X X X
Time of addition for each monomer is of the order of a millisecond.
Thus several thousands of additions can take place in a few
seconds.
 TERMINATION
• The last stage of chain reaction in which the growth of
the polymer chain terminated (or stopped).
• There are two mechanisms of termination
• 1. Combination
• Coupling together of two growing chains to form a single
polymer molecules. polystyrene
 --CH2-CH + CH - CH2--- ---- CH2-CH- CH-CH2---
 X X X X
 2. Disproportionation
 when a hydrogen atom move from one growing chain to
another
 H H
--CH -CH + C - C--- ----CH2-CH2 + CH=CH2---
2
 X X H X X
 Saturated end Unsaturated end
 group polymer group polymer
 RETARDATION AND INHIBITION
OF VINYL POLYMERIZATION: Role of inihibitors

• The rate of polymerization of vinyl monomers can be reduced or

almost completely inhibited by the addition of relative small
amounts of certain molecules, called retarders and inhibitors.
• Inhibitors are substances that almost completely suppress the
polymerization reaction.
• The induction time, which is the time between addition of initiator
and start of reaction (normal rate of reaction), is linear
proportional to the amount of inhibitor added.
• Retarders, on the other hand, only reduce the rate of
polymerization, that is, the rate of reaction steadily increases as
the retarder is consumed.
• The equivalent induction time of a retarder is the time that would
have been required for all the retarder to be consumed if it had
completely suppressed the reaction.
17
 INHIBITION VERSUS RETARDATION
• According to the general theory of inhibition,
inhibitors and retarders react with initiator
radicals to give products that are unable to
induce further polymerization.
• Retarders are less reactive than inhibitors and,
therefore, do not entirely prevent initiators from
reacting with monomers followed by the 
propagation reaction.
• Thus, a high concentration of retarder will
simulate the behavior of an inhibitor.
18
INHIBITION VERSUS • Typical conversion time curves
RETARDATION are shown in the figure. The
polymerization in the presence of
an inhibitor (blue curves) shows a
flat plateau with no or very low
reaction rates.
• At a certain point in time
(induction time) the reaction rate
rapidly increases to a value close
to the one found in the absence
of inhibitor.
• The retarder, on the other hand,
reduces only the rate of
polymerization (red curves). The
reaction rate increases steadily as
the retarder is consumed and
finally assumes its normal rate. 19
 Inhibition and Retardation
• The unintentional presence of retarders is often
the root cause for the irreproducible rates of
reaction of incompletely purified monomers,
that is, certain impurities can act as retarders or
inhibitors.
• In fact, it has been observed that a wide variety
of substances show a moderate retarding effect,
whereas only a small number of compounds
strongly retard or inhibit polymerization.
20
 Inhibitors
• Typical inhibitors are quinones and their derivatives and
sterically hindered phenols.
• These compounds strongly inhibit the polymerization of
vinyl monomers.
• Considerable induction times can be achieved with relative
small amounts of quinones.
• The main purpose of these compounds is to improve the
shelf-life of reactive monomer systems like curable coatings
and adhesives or to improve the heat and UV stability of
polymers, i.e. they act as stabilizers.
• They can also be added at larger concentration to delay
cure, i.e. to adjust the open-time and pot-life.
21
 Retarders
• Common retarders are nitro- or nitroso-derivatives of aromatic
compounds.
• These molecules have a strong retarding effect on many vinyl monomers,
and in a few cases, act as inhibitors. A prominent example for the later is
vinyl acetate.
• Other strong retarders or inhibitors for many vinyl monomers are
oxygen, iodine, and sulfur. Many investigations suggest that sequences of
-[-M-O-O-]- or -[-M-S-S-]-
appear in the polymer which are produced by a reaction of the form
R· + O2 → ROO·
• These chain radicals preferentially undergo chain termination, but
propagation also occurs because oxygen and sulfur have been found in
the polymer as well, however at a relative low concentration.
• Thus oxygen in the air can inhibit polymerization, particularly at the air-
monomer interface. This phenomenon is widely known as air inhibition.
22
 Syllabus
UNIT I (Chain Polymerization)
Free radical polymerization, Role of inihibitors and
retarders, Controlled radical polymerization - Iniferters
- Atom transfer radical polymerization (ATRP) Nitroxy
radical mediated (NMP) polymerization - Reversible
addition-fragmentation chain transfer (RAFT)
polymerization. Anionic and cationic polymerizations
Living polymerization, Ring opening polymerization,
Co-ordination polymerization, Zieglar Natta catalysts,
Single site catalysts, Copolymerization, Kinetics of
polymerization and copolymerization.
 Free Radical Initiated Polymerization

• Controlled Free Radical Polymerization

• Broad range of monomers available
• Accurate control of molecular weight
• Mw/Mn  1.05 --Almost monodisperse
• Blocks, telechelics, stars
(Controlled molecular architecture)
• Statistical Compositions and Sequences

24
Free Radical Polymerizations

25
 Otsu et al 1982
Iniferter approach

hn

recombination

exhibit living characteristics at low conversion, but PDI is broad as 3 can also
initiate polymerizations. 26
 The Key Concept in Living Radical Polymerization
PDI= Mw/Mn=1+qM0/Mn = 1+q/n
(Poisson distribution PDI = 1+1/n)

formation of dormant propagating species

reduces the effective polymeric radical
concentration and hence minimize
termination reactions
R∙ is a capping agent
and does not initiate
chain growth
Conventional
Radical Polymerization
Molecular Weight

Living Polymerization

Step Polymerization

Conversion (%) 27
 Stable Free Radical Polymerization (SFRP)
or Nitroxide Mediated Polymerization (NMP)
SFRP Initiator System (e.g., biomolecular or unimolecular)

+ Radical initiator
(BPO, AIBN) O
N

28
 Stable Free Radical Polymerization (SFRP)
Bimolecular Initiator System

29
 Stable Free Radical Polymerization (SFRP)
Unimolecular Initiator System

30
 State of Art for SFRP

•MW > 105, PDI = 1.1-1.2

•High reaction temperature (125-145oC) lower temperature
•Long reaction time (24-72 hr) (60-80oC), shorter
•Low to moderate conversion (<70%) reaction time (several
•Limited scope of monomers: St, MA, hrs) and higher
MMA etc. conversion (>99%) are
•functionalized alkoxyamine is required desired
for block or telechelic polymer synthesis

31
32
Atom Transfer Radical Polymerization (ATRP)

most common

Example:

Basic components: vinyl monomers, metal catalyst/ligand and initiator 33

Atom Transfer Radical Polymerization (ATRP)

Keq

ki

Keq’

kp

R'

34
 State of Art for ATRP
•MW > 105 easily, PDI = 1.1-1.6
•reaction temperature (70-130oC)
•Low to moderate conversion (<80%)
•Tolerant of functional groups, wide scope of monomers: St,
MA, MMA, acrylamide, vinylpyridine (VP), acrylonitrile (AN)
etc. (acrylic acid, vinyl halide, vinyl ether, a-olefin cannot be
polymerized)
•Availability of a variety of initiator and catalysts.
•block polymers and telechelic polymers are readily prepared.
•metal contaminant is sometime less desired

35
 Reversible Addition-Fragmentation Transfer
Polymerization (RAFT)
SFRP (NMP) and ATRP involves reversible termination

RAFT involves reversible chain transfer

36
 Reversible Addition-Fragmentation Transfer
Polymerization (RAFT) Mechanism

Stability
can be
controlled
by Z
group

Basic components: vinyl monomers, radical initiator and RAFT chain transfer agent.
The number of growing chain is determined by both CTA and initiator content.37
 RAFT Chain Transfer Agent
Design of CTA structures allows for control of the
relative rate of addition and fragmentation steps

RAFT polymerizations are compatible with a variety of activated (St, MMA, MA

etc.) or unactivated vinyl monomers (VAc, NVP). RAFT is versatile and robust as
compared to SFRP and ATRP. But CTA agents need to be individually synthesized.
38
 Acknowledgement
•MIT OpenCourseWare: Synthesis of Polymers by Dr. Paula Hammond
http://ocw.mit.edu/courses/chemical-engineering/10-569-synthesis-of-polymers-fall-2006/lecture-notes/
•Note by USM Dr. Daniel Savin and Dr. Derek Patton
http://www.usm.edu/polymerkinetics/
•Note by LSU Dr. Daly
•Polymer Chemistry, 2nd edition, Hiemenz and Lodge
•Principle of Polymerization, 4th edition, Odian
•Polymer Chemistry, 4th edition, Pan, Zheijiang University

•“Functional Polymers via Anionic Polymerizations.” Akira Hirao, 1997 ACS Symposium Series.
•“New Polymer Synthesis by Nitroxide Mediated Living Radical Polymerizations.” Craig Hawker, 2001, Chem. Rev.
•“Atom Transfer Radical Polymerization.” Krzysztof Matyjaszewski, 2001, Chem. Rev.
•“Copper(I)-Catalyzed Atom Transfer Radical Polymerization.” Krzysztof Matyjaszewski and Timothy Patten, 1999, Acc.
Chem. Res.
•“Toward Living Radical Polymerization.” Graeme Moad, Ezio Rizzardo, San Thang, 2008, Acc. Chem. Res.
•“Living Radical Polymerization by the RAFT Process.” Graeme Moad, Ezio Rizzardo, San Thang, 2005, Aust. J. Chem.
•“Living ring-opening metathesis polymerization catalyzed by well-characterized transition-metal alkylidene
complexes.” Richard Schrock, 1990, Acc. Chem. Res.
•“The Development of L2X2RuCHR Olefin Metathesis Catalysts: An Organometallic Success Story.” Robert Grubbs, 2001,
Acc. Chem. Soc.
•“Organocatalytic Ring-Opening Polymerization.” Robert Waymouth, James Hedrick, 2007, Chem. Rev.
•“Controlled Ring-Opening Polymerization of Lactide and Glycolide.” Didier Bourissou, 2004, Chem. Rev.
•“Synthesis of Well-Defined Polypeptide-Based Materials via the Ring-Opening Polymerization of α-Amino Acid N-
Carboxyanhydrides.” Nikos Hadjichristidis, 2009, Chem. Rev.

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