3.

Chain growth polymerization

1
 Chain-growth polymerization
 The polymerization of unsaturated monomers typically involves a
chain reaction. In a chain polymerization, one act of initiation may
lead to the polymerization of thousands of monomer molecules.
 The chain polymerization starts with an active center responsible for
the growth of the chain which is associated with a single polymer
molecule through the addition of many monomer units. Thus
polymeric molecules are formed from the beginning, and almost no
intermediate species between monomer and high molecular weight
polymer are found.
 Chain polymerization is initiated by a reactive species R* produced
from an initiator I:
The reactive species, which may be a free radical, cation, or anion,
adds to a monomer molecule by opening the p-bond to form a new
radical, cation, or anion center.

2
 Cont…
• The process is repeated as many more monomer molecules are
successively added to continuously propagate the reactive center as
the following:

• Polymer growth is terminated at some point by destruction of the

reactive center by an appropriate reaction depending on the type of
reactive center and the particular reaction conditions.

3
 Chain-Growth Polymerization
1. Only growth reaction adds repeating units one at a time to the chain
2. Monomer concentration decreases steadily throughout the reaction
3. High Molecular weight polymer is formed at once; polymer
molecular weight changes little throughout the reaction.
4. Long reaction times give high yields but affect molecular weight little.
5. Reaction mixture contains only monomer, high polymer, and about
10-8 part of growing chains.
6. Requires short reaction time and occurs at low reaction temperature
7. In the reaction only monomer and propagation species can react.

Step-Growth Polymerization
1. Molecular weight increases steadily.
2. High molecular weight polymers are found at the end.
3. Long reaction time needs to synthesize high conversion and high
molecular weight.
4
 Chain-growth Polymerization

Chain-Growth Polymerization (Addition) Processes

1. Free radical Initiation Processes

2. Cationically Initiated Processes

3. Anionically Initiated Processes

4. Group Transfer Polymerization

5. Coordination Polymerization

5
Chain Growth Polymerization
(1) Initiation

I. kd : Initiator decomposition rate constant

: 10-4 ~ 10-6 L/mole sec

Bond Energy = 46 kcal/mole

Heat (60ºC)
UV kd
AIBN Primary radical

Unstable radical

Ri  ki M I 
6
Chain Growth Polymerization

(2) Propagation (Repetition of similar reaction)

R p  k p M M 

kp : 102 ~ 104 L/mole sec (much faster than step-growth polymerization)

7
Chain Growth Polymerization

(3) Termination

(a) Coupling or combination

8
Chain Growth Polymerization

(3) Termination
(b) Disproportionation

ktd

ktd

kt=ktc+ktd 106 ~ 108 L/mole sec

Rt  k k M M   Rt M 
2

9
Chain Growth Polymerization
(4) Chain Transfer

Physical chain length

Monomer, Polymer, Solvent or Chain transfer agent

Kinetic chain length

10
Chain Growth Polymerization

Kinetic Chain Length :

kinetic chain length υ of a radical chain polymerization is defined as the
average number of monomer molecules consumed (polymerized) per
each radical, which initiates a polymer chain.
Radical
ex) Monomer # 4000 Disproportionation
1,2,3,4

υ =4,000/4 =1,000
Determined by steps 1, 2, 3. (Initiation, propagation, and termination)
(No chain transfer)

Physical Chain Length :

This condition contains Step 1, 2, 3, 4.

11
Kinetic Chain Reaction

Non-Polymerization Reaction

Peroxide induced Bromination of Toluene

1) Initiation
Two types of reaction
 R-O-O-R 2RO• (1)
 R-O• + Br2 ROBr + Br• (2)
 R-O• + ФCH3 ROH + ФCH2• (3)

Two radicals and two kinetic chains are formed by decomposition of

each ROOR molecules

12
Kinetic Chain Reaction

2) Propagation
 Br• + ФCH3 HBr + ФCH2 (4)
 ФCH2• + Br2 ФCH2Br + Br • (5)

Two special features

 The number of active species is fixed.
 Same reactions are repeated during the kinetic chain reaction.

13
Kinetic Chain Reaction

3) Termination
 2 Br• Br2
 2ФCH2• ФCH2 CH2Ф
 ФCH2• + Br • ФCH2Br + Br •

Net Effect of Kinetic Chain Reaction:

One ROOR molecule can cause formation of Br2, CH2CH2, CH2Br,HBr, ‥.

14
Kinetic Chain Reaction

Comparison between Chain Polymerization & Chain Reaction

Chain reaction Ri = Rt
Reaction Rate

Steady state

Time
Induction period

15
Kinetic Chain Reaction

In the case of Chain reaction, there are induction periods, due to the
existence of inhibitor.
When an active center is formed, the reaction rate would be faster and then
go to steady state.
The whole reaction rate is reaching a plateau region.
After that, reaction rate decreases due to a loss of monomers or initiators.
Linear Chain-Growth:
Polymer of high DPn found easily in early reaction
Linear Step-Growth:
high extent of reaction value required to obtain high DPn

16
 Kinetic Chain Reaction

Comparison of Free Radical Reaction & Ionic Reaction

- Ionic Initiation – multiple bond addition, ring opening polymerization

- Radical Initiation – Ring-opening polymerization is not initiated.

CH3 CH2 For the cationic initiation, it will not be free radical.

CH3
isobutylene

Ex)
CH2 H2C
CH3
CH2
R + CH2 H + CH2
H3C
H3C
H3C Because of resonance stability

17
 Kinetic Chain Reaction
Comparison between Free Radical Reaction & Ionic Reaction
Ionic Free Radical
Anionic Cationic
Ring opening + - -
End-groups Generally, combine with counter-ion
E.g. R+ AlCl4―
Degree of association depends on below
Solvent-system polarity Truly Free Radical
Stability of end group (no association)
Type & size of scounter-ion
Temp.

Degree of association influences:

Reaction rates
Termination rate
Stereospecificity
Termination Depend on monomer unimolecular Combination or Bimolecular
consumption, Living polymer or disproportionation reaction combination or
Block copolymer disproportionation

18
 Kinetic Chain Reaction
Comparison between Free Radical Reaction & Termination Step of Ionic Reaction

A) Free Radical Termination

. .CH CH ..
H
. .CH
CH2 CH CH CH
2
CH2
X X X X

ktc (coupling ktd (disproportionation)

or combination)

H
CH2 CH CH CH2
X X
CH CH + CH CH2
X X

Two molecules involved unsaturated group.

= bimolecular reaction

19
 Kinetic Chain Reaction
B) Cationic Termination
+
-
CH2 CH [XY]
R -
EX) AlCl4 檜 唳辦
-
X= Cl Y= AlCl3
X
CH2 CH + Y
R

Anionic capture is similar to combination of free radical reaction.

But, this reaction can’t include increasing of MW because of unimolecular reaction

20
 Kinetic Chain Reaction
C) Anionic Termination

..H
+ -
CH + [XY] X
+ HY + Y
proton release R
R
The proton release is similar to disproportination of free radical..
But, one chain joins in the reaction unimolecular reaction

C) Anionic Termination
Termination is rare but can occur by loss of a hydride ion
- +
CH 2
CH M
R
-
-H

CH CH + HM
R

Unimolecular type termination occurs

21
 Kinetic Chain Reaction
Anionic Cationic Free Radical
Termination Termination Termination
Reaction rate Unimolecular Bimolecular
High concentration of growing Relativity low
chains 10-2~10-3molar concentration 10-8~10-9
Rates 104~105 times higher than free molar occurs at high
radical Rates
E Activation Energies Similar
Chain Transfer Negligible + +
Disadvantage Rigorous Purity or precautions
Polymer System Solution or Bulk Wide variety of
polymer systems,
Gas, Solid, Solution,
Bulk, Precipitation,
Suspension, Emulsion

22
 Initiators of Radical Chain Polymerization
• Radical initiator's classified into three major types:
1. thermal initiators including peroxides and azo compounds,
2. Redox initiators
3. photo initiators, certain compounds that form radicals under
influence of light.
 Electrons can be used as initiating agent to generate radical ions for
chain polymerization.
1. Thermal Initiators: The most commonly used peroxide is benzoyl
peroxide , which undergoes thermal homolysis to form benzoyloxy
radicals.
Δ

23
 Cont…
• The benzoyloxy radicals may undergo a variety of reactions besides
adding to monomer, including recombination, decomposition to phenyl
radicals and carbon dioxide, and radical combination.
• These secondary reactions occur because of the confining effect of
solvent molecules (cage effect), and as a result, the concentration of
initiator radicals is depleted. Another ‘‘wastage’’ of initiator reaction is
induced decomposition.

24
 Cont…
• Two other common peroxide initiators are diacetyl peroxide 2 and di-
t-butyl peroxide 3.

• Hydroperoxides such as cumyl hydroperoxide 4 decompose to form

alkoxy and hydroxyl radicals.

• The extent of side reactions depends on the structure of peroxide,

the stability of the initially formed radicals, and the reactivity of the
monomers.
25
 Cont…
• α,α’-Azobis(isobutyronitrile) , is the most widely used azo compound
which decomposes at relatively low temperatures. The driving force
for decomposition is the formation of nitrogen and the resonance-
stabilized cyanopropyl radical. The initially formed radicals can also
combine in the solvent cage to deplete initiator concentration as with
the peroxide decomposition. The combination of the radicals leads to
both tetramethylsuccinonitrile and the ketenimine.
• Stability of the initators expressed by the half-life.

26
 Decomposition Temperature and Half-Life of Thermal Initiators
• The thermal, homolytic dissociation of initiators is the most widely
used mode of generating radicals to initiate polymerization for both
commercial polymerization and theoretical studies. Polymerizations
initiated in this manner are often referred to as thermal initiated or
thermal catalyzed polymerizations.
• Thermal initiators are usually having dissociation energies in the
range 100–170 kJ mol-1.
• Compounds with higher or lower dissociation energies will dissociate
too slowly or too rapidly.
Only a few classes of compounds—including those with O–O, S–S, or
N=N bonds—possess the desired range of dissociation energies.
• The differences in the decomposition rates of various initiators are
conveniently expressed in terms of the initiator half-life (t1/2) defined
as the time for the concentration of I to decrease to one half its
original value.
27
 Cont…
• The rate of initiator disappearance is

with integration yields

where [I]o is the initiator concentration at the start of polymerization.

t1/2 is obtained by setting [I] = [I]o/2, then

28
 Initiation Promoters
• Decomposition of peroxides can be induced at lower temperatures by
the addition of promoters. For example, addition of N, N-
dimethylaniline to benzoyl peroxide causes the latter to decompose
rapidly at room temperature. Kinetics studies indicate that the
decomposition involves formation of an unstable ionic intermediate
that reacts further to give benzoyloxy radical and a radical cation.

29
 Redox Initiators
• The redox initiators are useful in initiation of low temperature
polymerization and emulsion polymerization.
• Reaction rates are easy to control by varying the concentration of
metal ion or peroxide.
For nonaqueous polymerization, metal ions: Co2+ , Mn2+ , Cu2+ , and
Fe2+ are generally introduced.

30
 Photo initiators
• Peroxides and azo compounds dissociate photolytically as well as
thermally. The major advantage of photo initiation is that the reaction
is essentially independent of temperature.
• Control of the polymerization reaction is generally possible because
narrow wavelength bands may be used to initiate decomposition (less
side reactions), and the reaction can be stopped simply by removing
the light source.

31
 Electrochemical Initiation
• Electrolysis of a solution containing both monomer and electrolyte
can be used to initiate polymerization.
• At the cathode an electron may be transferred to a monomer
molecule to form a radical anion and at the anode a monomer
molecule may give up an electron to form a radical cation. The
radical ions in turn initiate free radical or ionic polymerization or
both, depending on electrolysis conditions.

32
 Techniques of Free Radical Chain Polymerization
• Free radical polymerization can be accomplished in bulk, suspension,
solution, or emulsion.
• Ionic and other nonradical polymerizations are usually confined to solution
techniques.
1. Bulk Polymerization
 The bulk polymerization is the simplest polymerization reaction without
contamination of solvent and other impurities or using especial equipment.
However, it is usually difficult to control due to the exothermic
polymerization reaction.
 When polymer is insoluble in monomer, polymer precipitates and the
viscosity of the medium does not change appreciably. The polymer droplet
may contain free radicals that can lead to autoacceleration—a rapid increase
in the polymerization rate.
 The bulk polymerization is usually used in the casting large sheet of PMMA
plastics or in the low molecular weight polymers synthesis for applications
in adhesives, plasticizers, tackifiers, etc.
33
 2. Suspension Polymerization
• The suspension polymerization involves mechanically dispersing
monomer in a noncompatible liquid, usually water. Then, the
resultant monomer droplets are polymerized by use of a monomer
soluble initiator.
• Monomer is kept in suspension by continuous agitation and the use of
stabilizers such as polyvinyl alcohol or methyl cellulose (ether).
Granular beads are obtained which are easy to handle and can be
isolated by filtration, etc. Polystyrene, poly(vinyl chloride), and
poly(methyl methacrylate) have been prepared by this method.

34
 3. Solution Polymerization
• Like suspension, solution polymerization allows efficient heat
transfer.
• Solvent must be chosen carefully to avoid chain transfer reactions
that may limit the growth of molecular weight of polymer.
• Apart from the environmental concerns associated with organic
solvents, a major problem in solution polymerization is
that it is often difficult to remove solvent.
• As a result, supercritical carbon dioxide has been used to do the
polymerization as a solvent. However, it is only suitable for polar
monomers such as acrylates; there is need for more development
work for other monomers.

35
 4. Emulsion Polymerization
• Emulsion polymerization and suspension polymerization are two water-based
heterogeneous polymerizations that are used extensively to control the thermal,
viscosity, and environmental problems of polymer industry. However, they are quite
different in the components and behaviors in the polymerization.
• The major difference between the two polymerizations is the reaction site, micelle
for emulsion polymerization, and monomer for suspension polymerization.
When the concentration of a surfactant exceeds its critical micelle concentration
(CMC), the excess surfactant molecules aggregate together to form small colloidal
clusters called micelles.
• Typical micelles have dimensions of 2–10 nm, with each micelle containing 50–150
surfactant molecules.

36
Comparison of free radical polymerization technique

37
 Kinetics of Free Radical Chain Polymerization
The initiation step:
 homolytic dissociation of an initiator species I.
 Initator combination with monomer.

 The rate of monomer disappearance (the rate of polymerization), is

given by • Each addition create a new radical higher by
one monomer unit.
where Ri and Rp are the rates of initiation and propagation, respectively.
• monomer molecules reacting in the initiation step
is far less than the number in the propagation step
for a process producing high polymer.

38
 Cont…
•The polymerization rate with radical concentration is not directly usable
since [M.] very low ∼10-8 and therefore it is desirable to
eliminate [M.]. In order to do this, one can use steady-state assumption:
the concentration of radicals increases initially, but almost
instantaneously reaches a constant, steady-state value. i.e Δ[M.]∼0,
during the course of polymerization. Therefore, the rates of initiation
Ri and termination Rt of radicals are equal .

39
 Efficiency factor

• Initiator efficiency (f): 0.5<f<1.0

mole fraction of initiator fragments that actually initiate polymer chains.
d [ M ]
Ri 
dt
 ki [ I ][ M ]
by convention, two radical formation
 2 fk d [ I 2 ]
f  1 Ri is unrelated with [M]
f=[M]
f < 1 Ri is related with [M]

[M] , f
[I2] , f due to induced decomposition

40
 Rate of Polymerization
• The rate of polymerization equation can be modified to include the
initiator efficiency (f).
• The equation indicates the polymerization rate is proportional to the
square root of initiator concentration and to the first power of
monomer concentration. Thus, doubling the initiator concentration
causes the rate to increase by a factor of about 1.4.

41
• Average kinetic chain length, ν-, which is defined as the average
number of monomer units polymerized per chain initiated, which is
equal to the rate of polymerization per rate of initiation.
Since Ri = Rt under steady-state conditions

• Substituting Rp and Rt

• Substituting the expression for [M.]

42
Kinetic Chain Reaction

Propagation
d[M ]
Rp    k p [ M ][ M ]
dt
kp
I   M  IM 2 
kp
             IM n 
Termination
M. .M

ktc ktd
d [ M ]
Rt    2( k tc  k td )[ M ]2
dt
By convention
Since 2 radical elimination
43
 Kinetic Chain Reaction

Overall Rate of Polymerzation

R o  k i [I][M]  k p [M][M]
(# of propagation step >>> # of initiation step)

R o ~ R p  k p [M][M]

Radical concentration

• Difficulty of measurement, low concentration. (~10-8molar)

• Thus, it is impractical using this therm.

• [M] elimination is desirable.

44
Kinetic Chain Reaction
[M] elimination methods
Steady-State Assumption

Radical concentration increases at the start, comes to steady state simultaneously

and then reaction rate change becomes 0. (active centers created and destroyed at the same time)
Ri = Rt

2 fk d [ I 2 ]  2( ktc  ktd )[M ]2

1 1
fk d
[ M ]  ( ) 2 [ I 2 ]2
ktc  ktd
1
R
or  [ i ]2
2 Rt
d[M ]
R    k  [ M ][M ]
dt
1 1
fk
 k  [ M ][ I 2]2 ( d
)2
ktc  ktd
45
 Synthesis of Commercial Polymers
• Polyethylene: radical chain polymerization of ethylene to polyethylene is
carried out at high pressures of 120–300 MPa and at temperature above the
Tm of polyethylene.
 The polyethylene produced by radical polymerization is referred to as low
density polyethylene (LDPE) or high-pressure polyethylene to distinguish it
from the polyethylene synthesized using coordination catalysts. The latter
polyethylene is referred to as high-density polyethylene (HDPE) or low-
pressure polyethylene.
 LDPE is more highly branched (both short and long branches) than high-
density polyethylene and is therefore lower in crystallinity (40–60 % vs. 70–
90 %) and density (0.91–0.93 g cm-3 vs. 0.94–0.96 g cm-3).
 LDPE has a wide range and combination of desirable properties. Its very
low T g of about -120 o C and moderately crystallinity and Tm of 105–110 o
C, give it flexibility and utility over a wide temperature range. Commercial
low-density polyethylenes have number-average molecular weights in the
range of 20,000–100,000.
46
 Cont…
Polystyrene: Continuous solution polymerization is the most important
method for the commercial production of polystyrene although suspension
polymerization is also used. Commercial polystyrene (PS) has number
average molecular weights in the range of 50,000–150,000.
Polyvinyl Chloride:
• Most poly(vinyl chloride) (PVC) is commercially produced by suspension
polymerization. A typical polymerization includes 180 parts water, and 100
parts vinyl chloride monomer, chain transfer agent (trichloro ethylene).
• The reactants are then heated in the closed system to about 50 oC, and the
pressure rises to about 0.5 MPa.
• Typical number-average molecular weights for commercial PVC are in the
range of 30,000–80,000.
Rigid pipe is used for home and construction, vinyl siding, window frames,
rain-gutter, packaging, and gloves.

47
 Cont…
Polyvinyl Acetate
• Polyvinyl acetate (PVAC) [–CH2–C(H)(O–CO–CH3)–]n is
synthesized from vinyl acetate monomer via emulsion or solution
polymerization.
• The Tg of PVAC is about 28 oC which is not very useful, but widely
used in water based paints, adhesives for papers, textiles, and wood.
• PVAC is also used for producing polyvinylalcohol (PVA) by
hydrolysis that is used as thickening agents, coatings, and adhesives.
Acryl Polymer
• Poly(methyl methacrylate) (PMMA) can be polymerized by bulk,
solution, suspension, and emulsion processes. PMMA is completely
amorphous but has high strength and excellent dimensional stability
due to the rigid polymer chains (Tg = 105 oC)
• They are softer since the polymer chains are not nearly as rigid [e.g.,
poly(ethyl acrylate) (PEA), Tg = -24 oC], due to the absence of the
methyl groups on alternating carbons of the polymer chains.

48
 Cont…
• Polyacrylonitrile ([–C–C(CN)–]n) (PAN) is synthesized by either
solution or suspension polymerization. Polyacrylonitrile contains
polar group to have high secondary force, so it exhibits good fiber
property.
• Fluoropolymers: The fluoropolymers are obtained mainly by
suspension polymerization; emulsion polymerization.
The most important members of this family are
poly(tetrafluoro ethylene) (PTFE), poly(chloro trifluoro ethylene)
(PCTFE), poly(vinyl fluoride) (PVF), and poly(vinylidene fluoride)
(PVDF).
• High molecular weight PTFE is usually obtained due to lack of chain-
transfer reactions and precipitation of growing radicals (leading to
greatly decreased termination). Fluoropolymers can withstand a wide
variety of chemical environments and are useful at temperatures as
low as -200 oC and as high as 260 oC.
49
 Chain Transfer Reactions
• Chain transfer reactions are the process transferring the growing
polymer chain to another species which terminates the chain, but at
the same time generates a new radical.
• The chain transfer reactions result in low molecular weight polymer
and broad molecular weight distributions.
• Chain transfer can occur among polymer, monomer, initiator, solvent
in the reaction mixture.

• Hydrogen abstraction may also occur intramolecularly, a process

referred to as backbiting or it may take place with solvent.

50
 Cont…
• Polystyrene prepared in carbon tetrachloride, for example, contains
chlorine at the chain end of polymer due to chlorine transfer and
initiation by the resultant .CCl3 radicals. Chain transfer is effective to
control M.Wt of polymer.

51
 Cont…
• When a chain transfer agent is used in polymerization, it is necessary to redefine the
kinetic chain length as being the ratio of propagation rate to the combined rates of
termination and transfer, as

• Since transfer reactions are second order, with

• where T is the transfer agent, one can rewrite the expression for mtr, taking into
account all possible transfer reactions, as

• It is known that then 1/v-tr

The ratio of the transfer rate constant to that of propagation is commonly defined
as the chain transfer constant, CT, for a particular monomer:

52
 Cont…
• As the rate of transfer and concentration of the transfer agent increase,
the kinetic chain length becomes progressively smaller.
Living Polymerization
 When the termination reaction is not present in the polymerization of
monomers, we call the polymerization is living polymerization. The
average degree of polymerization is simply equal to the ratio of the
initial monomer concentration to the initiator concentration.

 Living Radical Polymerization:

The living radical polymerization is also called controlled radical
polymerization.
The formal IUPAC name of this type of polymerization is called
reversible deactivation radical polymerization (RDRP)

53
 Cont…
• The living radical polymerization can be achieved by minimizing
normal bimolecular termination and prolonging the lifetime of living
polymers. Special mode of reaction for the propagating radicals by
either reversible termination or reversible transfer has been developed

54
 Atom Transfer Radical Polymerization
• The reactions of atom transfer radical polymerization (ATRP),
involves an atom transfer, usually a halogen atom, to form
propagating radicals and dormant species from the complex of atom
transfer agent and copper (I) catalyst.

55
 Nitroxide-Mediated Polymerization (NMP)
• The TEMPO is too stable to initiate polymerization, but it does
promote decomposition of benzoyl peroxide to benzoyloxy radicals
which initiate chain growth. Then TEMPO combines reversibly with
the growing polymer chain ends which protect the chain end radicals
from termination.

56
 Radical Addition-Fragmentation Transfer (RAFT)
 RAFT living polymerizations control chain growth through reversible
chain transfer.
 A chain transfer agent R’CSSR, such as cumyl dithiobenzoate
reversibly transfer a labile end group (a dithioester end group) to a
propagating chain. The polymerization is carried out with a
conventional initiator such as a peroxide or AIBN in the presence of
the chain-transfer agent.

57
 Temperature Effect of the Free Radical Polymerization
• By varying the polymerization temperature, there is big effect on the
rate and degree of polymerization.
• When the temperature increases, the rate of polymerization increases,
but the degree of polymerization decreases.
• Activation Energy and Frequency Factor:
The quantitative effect of temperature on rate of polymerization (Rp)
and degree of polymerization is very complex since they depend
on a combination of three rate constants of initiation (kd ) propagation
(kp)and termination (kt).
• Each of the rate constants can be expressed by an Arrhenius equation

• where A is the collision frequency factor, E the Arrhenius activation

energy, and T the kelvin temperature. A plot of ln k versus 1/T allows
the determination of both E and A from the slope and intercept,
respectively. 58
 Thermodynamics of Free Radical Polymerization
• The thermodynamics of free radical polymerization can be expressed
by ΔGp = ΔHp-TΔSp. The ΔGp, ΔHp, and ΔSp for a polymerization are
the difference in free energy, enthalpy, and entropy, respectively,
between 1 mol of monomer and 1 mol of repeating units in the
polymer product.
 The thermodynamic properties of a polymerization relate only to the
propagation step, since polymerization consists of single acts of
initiation and termination and a large number of propagation steps.
 Chain polymerizations of alkene are exothermic (ΔHp is ‘‘negative’’)
and exoentropic (ΔSp is ‘‘negative’’). The exothermic nature of
polymerization arises because the process involves the exothermic
conversion of π-bonds (less stable) in monomer molecules into σ-
bond (more stable) in the polymer. The negative ΔSp for
polymerization arises from the decreased degrees of freedom for the
polymer relative to the monomer. Thus, polymerization is favorable
from the enthalpy viewpoint, but unfavorable from the entropy
viewpoint. 59
 Ceiling Temperature
• The reversibility of polymerization reactions has been observed
which depends on the monomer reactivity and the stability of
polymer radical as shown in the following:

• where kdp is the depropagation rate constant. Just as radical stability

retards propagation, it enhances depropagation. As the polymerization
temperature is raised, the depropagation rate increases until a point is
reached where the forward and back reactions are equal. The
temperature at which this occurs is called the ceiling temperature
(Tc), and at that temperature ΔG of polymerization is zero, or

60
 Anionic Polymerization
• Anionic polymerization is defined as a chain reaction polymerization
in which the active centers for propagation are anions, which can be
in the form of free ions, paired ions, or aggregated species.

Living Anionic Polymerization

 It is a chain polymerization in which chain termination and
irreversible intermolecular chain transfer are absent; it should be
noted that chain termination is defined as a chemical reaction in
which a chain carrier is converted irreversibly into a nonpropagating
species without the formation of a new chain carrier.
 Provide methodologies for the synthesis of polymers with control of
molecular weight, molecular weight distribution, copolymer
composition and microstructure, stereochemistry, chain-end
functionality, and molecular architecture.
61
Mechanism of anionic polymerization

Scheme. General mechanism for a

living anionic polymerization.

62