Chapter 7

Radical Chain 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. Table 7.1 lists the characteristics of chain
polymerization as compared with step polymerization. The chain polymerization
starts with an active center responsible for the growth of the chain which is asso-
ciated with a single polymer molecule through the addition of many monomer units.
Thus polymeric molecules are formed from the beginning, and almost no inter-
mediate species between monomer and high molecular weight polymer are found.
Chain polymerization is initiated by a reactive species R* produced from an
initiator I:
I ! R ð7:1Þ
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. The process is repeated as many more monomer molecules are successively
added to continuously propagate the reactive center as the following:

H H H
H2 C CHY H2 C CHY
R* R CH2 C* R CH2 C CH2 C*
Y Y Y

H H
H 2C CHY
R CH2 C CH2 C*
Y n Y
ð7:2Þ

R*: Radical, cationic, anionic.

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.

W.-F. Su, Principles of Polymer Design and Synthesis, 137

Lecture Notes in Chemistry 82, DOI: 10.1007/978-3-642-38730-2_7,
Ó Springer-Verlag Berlin Heidelberg 2013
138 7 Radical Chain Polymerization

Table 7.1 Comparison of chain polymerization and step polymerization

Situation Chain polymerization Step polymerization
Molecular weight High molecular weight High molecular weight molecule
formed immediately, formed at the end of reaction,
doesn’t change with time change with time
Monomer concentration Change throughout the Only available in the beginning
course of the reaction of the reaction, then form
dimer, trimer, etc
Any time of the reaction Contain monomer, Beginning—monomer
high polymer, Middle—growing chain
and growing chain End—high polymer
Polymerization step Only monomer and propagation Any two molecules can react
species can react
Reaction time Short Long
Reaction temperature Low High

In this chapter, we only discuss free radical chain polymerization. The ionic
chain polymerization will be discussed in Chap. 8. Table 7.2 lists some common
free radical chain-growth polymers and their uses. The chain-growth polymers
count more than 80 % total usage of polymers in our daily life.

7.1 Effect of Chemical Structure of Monomer

on the Structural Arrangement of Polymer

There are two possible points of attachment on monosubstituted (X = H) or 1,1-

disubstituted monomers for a propagating radical, either on carbon 1 to form I or
on carbon 2 to form II as the following:

X X

R + C CH2 R C CH2
ð7:3Þ
Y Y

X X

R + H 2C C R CH 2 C
ð7:4Þ
Y Y

II

If each successive addition of monomer molecules to the propagating radical

occurs in the same manner as Eqs. 7.3 or 7.4, the final polymer product will have
Table 7.2 Some commercial chain-growth (vinyl) polymers prepared by free radical polymerization [1, 2]
Monomer name Formula Polymer Uses
Ethylene (ethene) H 2C CH 2 Polyethylene Sheets, films, bottles, toys and house wares, wire and cable, coverings,
shipping containers, insulation
Propylene (propene) H2 C CHCH 3 Polypropylene Carpeting, car and truck parts, packaging, toys, house wares, pipes,
insulation
Styrene Polystyrene Packaging and containers (Styrofoam), toys, appliance parts,
H2C CH
disposable food containers and utensils, insulation
Acrylonitrile (propenenitrile) H 2C CHCN Polyacrylonitrile (Orion, Sweaters, clothing, fiber
7.1 Effect of Chemical Structure of Monomer

Acrilan)
Vinyl acetate (ethenyl O Poly(vinyl acetate) Adhesives, latex paints
ethanoate) H 2C CH OCCH 3
Methyl methacrylate (methyl 2- O Poly(methyl methacrylate) Lens, windows, coatings
methylpropenoate) H 2C CCH3 COCH 3 (Plexiglas, Lucite)
Vinyl chloride (chloroethene) H2 C CHCl Poly(vinyl chloride)(PVC) Plastic pipe and pipe fittings, films and sheets, floor tile, records,
coatings, building materials, insulation
Tetrafluoroethylene F2 C CF 2 Poly(tetrafluoro ethylene) Coatings for utensils, electric insulators, battery, solar cell
(tetrafluoroethene) (Teflon)
139
140 7 Radical Chain Polymerization

an arrangement of monomer units in which the substituents are on alternate carbon

atoms as shown in Eq. 7.5:

X X X X X X

CH 2 C CH 2 C CH2 C CH2 C CH 2 C CH 2 C
ð7:5Þ
Y Y Y Y Y Y

III

This type of arrangement III is usually referred to as a head-to-tail (H–T) or

1,3-placement of monomer units. An inversion of this mode of addition, by the
polymer chain propagating alternately via Eqs. 7.3 and 7.4, would lead to a
polymer structure with a 1,2-placement of substituents at one or more places in the
final polymer chain. The 1,2-placement is usually referred to as head-to-head (H–
H) placement as shown in Eq. 7.6.

head-to-head
X X X X X X

CH2 C CH2 C CH 2 C C CH 2 CH2 C CH2 C

ð7:6Þ
Y Y Y Y Y Y

tail-to-tail

The head-to-tail placement is predominant, since successive propagations by

Eq. 7.4 are favored on both steric and resonance grounds. The propagating radical
(radical II) formed by attachment of a radical at carbon 2 is the more stable one.
The radical II can be stabilized by the resonance effects of the X and Y substituents.
The substituents cannot stabilize radical I, since they are not attached to the carbon
bearing the unpaired electron. Furthermore, the attachment of a propagating rad-
ical at the unsubstituted carbon 2 of a monomer molecule is much less sterically
hindered compared with the attachment at the substituted carbon 1. A propagation
proceeding with predominantly H–T placement is a regioselective process, that is,
one orientation (H–T) is favored over another (H–H). The term isoregic has been
used to indicate a polymer structure with exclusive head-to-tail placements. The
terms syndioregic and aregic are used for polymer structures with alternating and
random arrangements, respectively, of H–T and H–H placements.
These theoretical predictions have been experimentally verified for a number of
polymers. The presence of no more than 1–2 % head-to-head placement in various
polymers of vinyl esters such as poly (vinyl acetate) has been determined by
hydrolysis of the polymer to poly(vinyl alcohol) and the periodate oxidation of the
1,2-glycol units (see Sect. 5.2.1). Other polymers with head-to-head arrangement
have been determined by 19F, 13C, and 1HNMR analysis.
The H–T propagation is indeed the predominant ([98–99 %) mode of propa-
gation in chain polymerization. For instance, the synthesis of styrene, there is no
7.1 Effect of Chemical Structure of Monomer 141

Table 7.3 The extent of H– Reaction % Head–Head

H replacement in fluoro
polymers [3] C=CF ? (–C–CF–)n 10
C=CF2 ? (–C–CF2–)n 5
CF=CF2 ? (–CF–CF2–)n 12
CFCl=CF2 ? (–CFCl–CF2–)n 2

Table 7.4 Reaction Polymer Temperature (°C) % Head–Head

temperature effect on the
extent of H–H replacement of Poly(vinyl acetate) 40 1
polymer [3] 100 2
Poly(trifluoro ethylene) -80 10
80 14

detectable H–H placement of polystyrene. The only exceptions occur when the
substituents on the double bond are small (and do not offer appreciable steric
hindrance to the approaching radical) and do not have a significant resonance
stabilizing effect, specifically when fluorine is the substituent. Table 7.3 shows the
extent of H–H placements of fluoro polymers.
By increasing the polymerization temperature, the extent of H–H placement is
increased, but the effect is small. Table 7.4 shows the compositions of polymers
with the effects from reaction temperature.
Some polymers consisting entirely of head-to-head (H–H) placements have
been deliberately synthesized to determine if significant property differences exist
compared to the head-to-tail polymers. The synthetic approach involves an
appropriate choice of monomer for the particular H–H polymer. For example, H–H
poly (vinyl chloride) was obtained by chlorination of 1,4-poly-1,3-butadiene
(Eq. 7.7).

Cl Cl
Cl2
CH2 CH CH CH2 CH2 CH CH CH2
ð7:7Þ
n n

H–H polystyrene was obtained by hydrogenation of 1,4-poly-2,3-diphenylbu-

tadiene (Eq. 7.8).

H2
CH 2 C C CH2 CH 2 CH CH CH 2
n n
ð7:8Þ
142 7 Radical Chain Polymerization

7.2 Initiators of Radical Chain Polymerization

Ideally, the initiators should be relatively stable at room temperature but should
decompose rapidly enough at polymer processing condition to ensure a practical
reaction rate. A large number of free radical initiators are available [2–4]; they may
be classified into three major types: (1) thermal initiators including peroxides and
azo compounds, (2) redox initiators, and (3) photoinitiators, certain compounds
that form radicals under influence of light. Electrons can be used as initiating agent
to generate radical ions for chain polymerization.

7.2.1 Thermal Initiators

The most commonly used peroxide is benzoyl peroxide 1, which undergoes

thermal homolysis to form benzoyloxy radicals (Eq. 7.9). The benzoyloxy radicals
may undergo a variety of reactions besides adding to monomer, including
recombination (reverse of Eq. 7.9), decomposition to phenyl radicals and carbon
dioxide (Eq. 7.10), and radical combination (Eqs. 7.11 and 7.12). 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 (Eq. 7.13).

O O O
C O O C 2 C O
ð7:9Þ

O
ð7:10Þ
C O + CO2

2 ð7:11Þ

O O
C O
ð7:12Þ
C O +
7.2 Initiators of Radical Chain Polymerization 143

O O
C O O C +

O O O O
C O O C C O + O C

ð7:13Þ

Two other common peroxide initiators are diacetyl peroxide 2 and di-t-butyl
peroxide 3.
O O CH3 CH3

H3C C O O C CH3 H3C C O O C CH3

CH3 CH3
2 3
Hydroperoxides such as cumyl hydroperoxide 4 decompose to form alkoxy and
hydroxyl radicals (Eq. 7.14). Because hydroperoxides contain an active hydrogen
atom, induced decomposition occurs readily, for example, by a chain-end radical
(Eq. 7.15). Peroxy radicals may also combine with subsequent formation of
oxygen (Eq. 7.16).

OOH
C(CH 3)2

4
ROOH RO + OH (7.14)

RO CH 2 CH CH 2 CH + ROOH RO CH 2 CH CH 2 CH 2 + ROO

R' n R' R' n R'

ð7:15Þ

2 ROO ROO OOR 2 RO + O2 ð7:16Þ

The extent of side reactions depends on the structure of peroxide, the stability
of the initially formed radicals, and the reactivity of the monomers.
a, a0 -Azobis(isobutyronitrile) 5, 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
(Eq. 7.17). The initially formed radicals can also combine in the solvent cage to
deplete initiator concentration as with the peroxide decomposition. The combination
144 7 Radical Chain Polymerization

of the radicals leads to both tetramethylsuccinonitrile 6 (Eq. 7.18) and the keteni-
mine 7 (Eq. 7.19).

CN CN CN

(CH 3) 2C N N C(CH 3) 2 2 (CH3 )2 C + N2

ð7:17Þ

CN CN (7.18)
(H3C)2C C(CH3)2
CN
6
2 (CH3) 2C
CN
(CH3) 2C C N C(CH3)2 (7.19)
7
The stability of thermal initiator is expressed by their half-life at different
temperature as discussed below.

7.2.2 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 peroxides are most
extensively used as radical sources. Several common peroxy compounds are
tabulated in Table 7.5.
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. The rate of initiator
disappearance is
d½I
¼ kd ½I ð7:20Þ
dt
7.2 Initiators of Radical Chain Polymerization 145

Table 7.5 Peroxides and their decomposition temperature [3]

Peroxide Decomposition
temperature (oC)
O O O 70–90
H3C C O O C CH 3 2 H3C C O

Acyl peroxide
O O O 80–95

C O O C 2 C O

Benzoyl peroxide
CH 3 CH3 CH 3 120–140

C O O C 2 C O

CH 3 CH3 CH 3

Cumyl peroxide
CH3 CH 3 CH 3 120–140

H 3C C O O C CH3 2 H3C C O

CH3 CH 3 CH 3
Di-t-butyl peroxide

with integration yields

½I  ¼ ½I0 ekd t ð7:21aÞ

or
½I0
ln ¼ kd t ð7:21bÞ
½I
where ½I0 is the initiator concentration at the start of polymerization. t1=2 is
obtained by setting ½I ¼ ½I 0 =2, then
0:693
t1=2 ¼ ð7:22Þ
kd
Table 7.6 lists the initiator half-life for several common initiators at various
temperatures. The peroxides are rather unstable. They should store in the refrig-
erator to prolong their shelf life. Azobis (isobutyronitrile), benzoyl peroxide, and
acetyl peroxide are decomposed at relatively low temperature, so they usually add
into monomer right before the polymerization to avoid any premature decompo-
sition and polymerization. t-Butyl peroxide and t-butyl hydroperoxide are
 146

Table 7.6 Half-life of initiators [3]

Initiator Half-Life at
50oC 60oC 70oC 85oC 100oC 115oC 130oC 145oC 155oC 175oC
Azobis (isobutyronitrile) 74 h 4.8 h 7.2 min
Benzoyl peroxide 7.3 h 1.4 h 19.8 min
Acetyl peroxide 158 h 8.1 h 1.1 h
Lauryl peroxide 47.7 h 12.8 h 3.5 h 31 min
t-Butyl peracetate 88 h 12.5 h 1.9 h 18 min
Cumyl peroxide 13 h 1.7 h 16.8 min
t-Butyl peroxide 218 h 34 h 6.4 h 1.38 h
t-Butyl hydroperoxide 338 h 44.9 h 4.81 h
7 Radical Chain Polymerization
7.2 Initiators of Radical Chain Polymerization 147

decomposed at high temperature. They can be mixed with monomer and stored in
room temperature without premature reaction for more than 3 months.

7.2.3 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 interme-
diate (Eq. 7.23) that reacts further to give benzoyloxy radical and a radical cation
(Eq. 7.24).

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

O CH3 O
C O N + C O

CH3
ð7:23Þ

O CH3 O H3C N CH3

C O N C O +

CH3
ð7:24Þ

7.2.4 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 con-
centration of metal ion or peroxide. For nonaqueous polymerization, metal ions:
Co2+, Mn2+, Cu2+, and Fe2+ are generally introduced as the naphthenates shown in
below. Cobalt naphthenate is commonly used as unsaturated polyester (Alkyd
resin) drying agents for the autoxidative crosslinking of the double bond.
148 7 Radical Chain Polymerization

n
Fe 2+

m
O

Iron Naphthenate
Some typical examples of redox initiators are given in Eqs. 7.25–7.27. They
have been used in the emulsion copolymerization of styrene and butadiene to form
styrene—butadiene rubber in low temperature. Hydrogen peroxide or persulfate
systems, Eqs. 7.26 and 7.27, are used in the emulsion polymerization. They can
produce radicals in an aqueous phase.

OOH O
2+
Fe3+
ð7:25Þ
C(CH3) 2 + Fe C(CH3) 2 + OH- +

HOOH + Fe 2 + HO + OH - + Fe3+ ð7:26Þ

-O SOOSO - + SO42- +
3 3 + S 2O 32- SO 4- S2O3 - ð7:27Þ

7.2.5 Photoinitiators

Peroxides and azo compounds dissociate photolytically as well as thermally. The

major advantage of photoinitiation is that the reaction is essentially independent of
temperature. Furthermore, better control of the polymerization reaction is gener-
ally possible because narrow wavelength bands may be used to initiate decom-
position (less side reactions), and the reaction can be stopped simply by removing
the light source. The reaction is fast (s vs. min) as compared to the thermal
initiation. A wide variety of photolabile compounds are available, including
disulfides (Eq. 7.28), benzoin 8 (Eq. 7.29), and benzyl 9 (Eq. 7.30). Table 7.7 lists
some commercial available photoinitiators and their decomposition wavelength. It
is interesting to note that most of the initiators contain benzoyl group which can
form stable benzoyl radical through the resonance stabilization of phenyl ring.
7.2 Initiators of Radical Chain Polymerization 149

Table 7.7 Commercial photoinitiators and their initiated wavelength [5]

Chemicals kmax ðnmÞ
1-hydroxy-cyclohexyl-phenyl-ketone 245
2-methyl-1-[4-(methylthio)phenyl)-2-(4-morpholinyl)-1-propanone 307
2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone 324

hν
RSSR 2 RS ð7:28Þ

O OH hv O OH

C CH C + CH ð7:29Þ

O O O
hν
C C 2 C ð7:30Þ

7.2.6 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 (Eq. 7.31), and at the anode a monomer
molecule may give up an electron to form a radical cation (Eq. 7.32). The radical
ions in turn initiate free radical or ionic polymerization or both, depending on
electrolysis conditions.

RHC CH2 + e- RHC CH2 ð7:31Þ

RHC CH2 RHC CH2 + e- ð7:32Þ

150 7 Radical Chain Polymerization

7.3 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. Each of the methods has advantages and disadvantages, as
outlined in Table 7.8.

7.3.1 Bulk Polymerization

The bulk polymerization is the simplest polymerization reaction without con-

tamination 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.

7.3.2 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

Table 7.8 Free radical polymerization techniques

Method Advantages Disadvantages
Bulk Simple; no contaminants added Reaction exotherm difficult to control;
high viscosity
Suspension Heat readily dispersed; low viscosity; Washing and/or drying required;
polymer obtained in granular form agglomeration may occur;
and may be used directly contamination by stabilizer
Solution Heat readily dispersed; low viscosity; Added cost of solvent; solvent difficult to
may be used directly as solution remove; possible chain transfer with
solvent; possible environmental
pollution
Emulsion Heat readily dispersed; low viscosity; Contamination by emulsifier and other
high molecular weight obtainable; ingredients; chain transfer agents
may be used directly as emulsion; often needed to control degree of
works on tacky polymers polymerization; washing and drying
necessary for bulk polymer
7.3 Techniques of Free Radical Chain Polymerization 151

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.

7.3.3 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.

7.3.4 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
comparison between the two polymerization processes is summarized in
Table 7.9. 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

Table 7.9 Comparison between suspension polymerization and emulsion polymerization [3]
Component/Characteristic Emulsion Suspension
Particle size 1–10 lm monomer 5–500 lm monomer droplets
2–10 nm micelle
Monomer/water ratio 30/70 to 60/40 25/75 to 50/50
Surfactant 0.2–3 % in micelle form 0.1 %
Initiator Water soluble Oil soluble
Water-soluble stabilizer None [1 %
Product particle size 0.05–0.2 lm 0.5–10 lm
Phase One Two
Polymerization site Micelle Monomer
152 7 Radical Chain Polymerization

clusters called micelles. Typical micelles have dimensions of 2–10 nm, with each
micelle containing 50–150 surfactant molecules. The largest portion of the
monomer ([95 %) is dispersed as monomer droplets whose size depends on the
stirring rate. Monomer droplets have diameters in the range 1–100 lm. Thus, in a
typical emulsion polymerization system, the monomer droplets are much larger
than the monomer-containing micelles. Consequently, while the concentration
of micelles is 1019–1021 L-1, the concentration of monomer droplets is at most
1012–1014 L-1. A further difference between micelles and monomer droplets is that
the total surface area of the micelles is larger than that of the droplets by more than
two orders of magnitude.
Polymerization takes place exclusively in micelle. Monomer droplets do not
compete effectively with micelles in capturing radicals produced in solution
because of the much smaller total surface area of the droplets. The micelles act as a
meeting place for the organic (oil soluble) monomer and the water-soluble initi-
ator. The micelles are favored as the reaction site because of their high monomer
concentration compared to the monomer in solution. As polymerization proceeds,
the micelles grow by the addition of monomer from the aqueous solution whose
concentration is replenished by dissolution of monomer from the monomer
droplets. A simplified schematic representation of an emulsion polymerization
system is shown in Fig. 7.1. The system consists of three types of particles:
monomer droplets, inactive micelles in which polymerization is not occurring, and
active micelles in which polymerization are occurring. The latter are no longer
considered as micelles but are referred to as polymer particles. An emulsifier
molecule is shown as s— to indicate one end (s) is polar or ionic and the other
end (—) is nonpolar.

Fig. 7.1 Simplified representation of an emulsion polymerization system [3]

7.4 Reaction Mechanism of Free Radical Chain Polymerization 153

7.4 Reaction Mechanism of Free Radical Chain

Polymerization

Two reactions are involved in the initiation of free radical chain polymerization:
formation of the initiator radical (Eq. 7.33), and addition of the initiator radical to
monomer (Eq. 7.34). The end group analysis of propagating chain shows the initi-
ator radicals are incorporated into the polymer. The propagation reactions comprise
addition of monomer radical to another monomer molecule, followed by successive
additions of oligomer and polymer radicals to available monomer (Eq. 7.35).

Initiator R ð7:33Þ

R + H 2C CH R CH2 CH
ð7:34Þ
Y Y

R CH2 CH + H2C CH R CH2 CH CH2 CH

Y Y Y Y

n H 2C CHY R CH2 CH CH2 CH CH2 CH

Y Y n Y
ð7:35Þ

Propagation continues until some reaction occurs to terminate it. Two radicals
are easily be terminated by a combination (coupling) reaction as shown in Eq. 7.36.

H H H H
k tc
CH 2C + CCH2 CH2 C C CH2 ð7:36Þ
Y Y Y Y

On the other hand, more rarely, they can be terminated by a disproportionation

reaction, in which a hydrogen radical that is beta to one radical center is trans-
ferred to another radical center. This results in the formation of two polymer
molecules—one saturated and one unsaturated as shown in Eq. 7.37:

H H
k td
CH CH + CH2 CH2
CH2 C + CCH 2
Y Y
Y Y
ð7:37Þ
154 7 Radical Chain Polymerization

The two different modes of termination can be represented in general term by

ktc
Mn  þMm  ! Mnþm ð7:38Þ
ktd
Mn  þMm  ! Mn þ Mm ð7:39Þ
where ktc and ktd are the rate constants for termination by coupling and dispro-
portionation, respectively. One can also express the termination step by
Mn  þMm  ! dead polymer ð7:40Þ
where the particular mode of termination is not specified and
kt ¼ aktc þ ð1  aÞktd ð7:41Þ
where a and ð1  aÞ are the fractions of termination by coupling and dispropor-
tionation, respectively.
Typical termination rate constants are in the range of 106–108 dL mol-1 s-1 or
orders of magnitude greater than the propagation rate constants. The much greater
value of kt (whether ktc or ktd ) compared to kp does not prevent propagation
because the radical species are present in very low concentrations and the poly-
merization rate is only dependent on the one half power of kt . Thus, whether
termination occurs by coupling or by disproportionation depends on monomer
structure or, more exactly, on the structure of the chain-end radical, e.g., steric
repulsion, electrostatic repulsion (raise the activation energy for coupling), and
availability of alpha hydrogen. Polystyryl radicals undergo coupling (Eq. 7.42)
almost exclusively at low temperatures, whereas poly(methyl methacrylate) radi-
cals undergo mainly disproportionation (Eq. 7.43). The polystyryl radical is more
reactive than methacrylate radical due to the resonance stabilization, so it will
undergo coupling instead of disproportionation.

H H H
2 CH 2 C CH2 C C CH2
ð7:42Þ
7.4 Reaction Mechanism of Free Radical Chain Polymerization 155

CH 3 CH 3 CH 3
2 CH 2C CH 2CH + CH C

CO2CH3 CO2CH3 CO 2CH3

ð7:43Þ
CH2
or CH 2 C
CO 2CH 3

Another possible termination reaction involves combination of initiator radicals

with chain end radicals (Eq. 7.44) called primary radical termination. This process
occurs at high initiator concentration or high viscosity that limits the diffusion of
polymer radicals.

CH2CH + R CH2CHR
ð7:44Þ
Y Y

7.5 Kinetics of Free Radical Chain Polymerization

Radical chain polymerization is a chain reaction consisting of a sequence of three

steps—initiation, propagation, and, termination. The initiation step involves two
reactions (Eqs. 7.45 and 7.46). The first is the production of free radicals by
homolytic dissociation of an initiator species I to yield a pair of radicals R
kd
I ! 2R ð7:45Þ
where kd is the rate constant for the catalyst dissociation. The second part of the
initiation involves the addition of this radical to the first monomer molecule to
produce radical M1 
ki
R  þM ! M1  ð7:46Þ
Propagation consists of the growth of Mn  by the successive additions of large
numbers (hundreds and perhaps thousands) of monomer molecules. Each addition
creates a new radical that has the same identity as the one previously, except that it
is larger by one monomer unit. The successive additions may be represented by
kp
Mn  þ M ! Mnþ1  ð7:47Þ
Monomer disappears by the initiation reaction (Eq. 7.45) as well as by the
propagation (Eq. 7.46). The rate of monomer disappearance, also called the rate
of polymerization, is given by
156 7 Radical Chain Polymerization

d½M
 ¼ R i þ Rp ð7:48Þ
dt
where Ri and Rp are the rates of initiation and propagation, respectively. However,
the number of monomer molecules reacting in the initiation step is far less than the
number in the propagation step for a process producing high polymer. Thus, the
rate of initiation can be neglected and the polymerization rate is given simply by
the rate of propagation. The rate of propagation, and therefore the rate of poly-
merization, is the sum of many individual propagation steps. Since the rate con-
stants for all the propagation steps are the same, one can express the
polymerization rate by
d½M
 ¼ Rp ¼ kp ½M½M ð7:49Þ
dt
where ½M is the monomer concentration and ½M is the total concentration of all
chain radicals, that is, all radicals of size M 1  and larger.
The polymerization rate (Eq. 7.49) is not directly usable because it contains a
term of radical concentration. Radical concentrations are difficult to measure
quantitatively, since they are very low (*10-8M), and it is therefore desirable to
eliminate ½M from Eq. 7.49. In order to do this, one can use steady-state
assumption: the concentration of radicals increases initially, but almost instanta-
neously reaches a constant, steady-state value. That means the rate of change of
the concentration of radicals is zero during the course of the polymerization.
Therefore, the rates of initiation Ri and termination Rt of radicals are equal

Rt ¼ Ri ¼ 2kt ½M2 ð7:50Þ

Rearrange Eq. 7.50 to obtain
 1=2
Ri
½M ¼ ð7:51Þ
2kt
and substitute Eq. 7.51 into Eq. 7.49 that yields the rate of polymerization
equation.

Rp ¼ kp ½MðRi =2kt Þ1=2 ð7:52Þ

7.5.1 Rate of Polymerization

The rate of polymerization equation can be modified to include the initiator effi-
ciency (f) as shown in Eq. 7.53. 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
7.5 Kinetics of Free Radical Chain Polymerization 157

Table 7.10 Representative propagation and termination rate constants, kp and kt [2]
Monomer Temperature (°C) kp kt 9 10-6
(L/mol-s) (L/mol-s)
Acrylonitrile 60 1,960 782
Ethylene 83 240 540
Methyl acrylate 60 2,090 9.5
Methyl methacrylate 60 515 25.5
Styrene 60 176 72
Vinyl acetate 50 2,640 116.8
Vinyl chloride 50 11,000 2,100
Tetrafluoroethylene 40 7,400 7.4 9 10-5

to increase by a factor of about 1.4. This relationship has been confirmed experi-
mentally for a variety of free radical polymerizations. Propagation and termination
rate constants, for several commercially important monomers are given in
Table 7.10. The tetrafluoroethylene has an extremely low kt which results in higher
molecular weight polymer as compared with the polymerization of ethylene.
sffiffiffiffiffiffiffiffiffiffi
fkd ½I
Rp ¼ kp ½M ð7:53Þ
kt

7.5.2 Average Kinetic Chain Length m

Another important parameter related to polymerization rate is the average kinetic

chain length, m, which is defined as the average number of monomer units poly-
merized per chain initiated, which is equal to the rate of polymerization per rate of
initiation. Since Ri ¼ Rt under steady-state conditions,
Rp Rp
m¼ ¼ ð7:54Þ
Ri Rt
Substituting for Rp and Rt into Eq. 7.54:
kp ½M ½M kp ½ M 
m¼ 2
¼ ð7:55Þ
2kt ½M 2kt ½M

Substituting the expression for ½M from Eq. 7.51,

kp ½M
m¼ ð7:56Þ
2ðfkt kd ½IÞ1=2
Kinetic chain length is related to a variety of rate and concentration parameters.
It will decrease as both of initiator concentration and initiator efficiency increase.
158 7 Radical Chain Polymerization

This is reasonable because increasing the number of growing chains increases the
probability of termination. Thus, varying initiator concentration can control
molecular weight. In the absence of any side reactions, kinetic chain length is
related directly to degree of polymerization depending on the mode of termination.
If termination occurs exclusively by disproportionation, DP ¼ m; if it occurs by
coupling, DP ¼ 2m.
Autoacceleration, a marked increase in polymerization rate, can occur at very
viscous medium even though the chain mobility is reduced and the termination is
reduced. The small monomer molecules can still diffuse to the active chain ends to
be polymerized. Autoacceleration may cause processing difficulties, particularly in
bulk polymerizations, because the increase in rate is usually accompanied by an
increase in reaction exotherm and gelation of polymer.

7.5.3 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. Equations 7.57 and 7.58 show
the polymer inter- and intrachain transfer reactions, respectively. A chain-end
radical may abstract a hydrogen atom from a chain, leading to a reactive site for
chain branching (Eq. 7.57).

CH + CH2CH CH2 + CH2C

Y Y Y Y

H 2C CHY

CH2CHY
CH2C

Y
ð7:57Þ

Hydrogen abstraction may also occur intramolecularly, a process referred to as

backbiting. Polyethylene, produced by high-pressure free radical polymerization
of ethylene, is highly branched through backbiting involving five- or six-mem-
bered cyclic transition states (Eq. 7.58). The properties of branched polymers are
expected to differ remarkably from those of the corresponding linear polymers as
we discussed in Chaps. 3 and 4.
7.5 Kinetics of Free Radical Chain Polymerization 159

CH 2 CH 2 CH 2 CH 2
CH C H2 CH CH 2 ð7:58Þ
H CH 2 CH 3

Chain transfer may also occur with initiator (Eq. 7.59) or monomer (Eq. 7.60),
or it may take place with solvent. Polystyrene prepared in carbon tetrachloride, for
example, contains chlorine at the chain end of polymer due to chlorine transfer
(Eq. 7.61) and initiation by the resultant CCl3 radicals (Eq. 7.62). Transfer to
monomer is particularly important with monomers containing allylic hydrogen,
such as propylene, because the formation of resonance-stabilized allylic radicals
(Eq. 7.63) is highly favorable. Thus, high-molecular-weight polypropylene cannot
be prepared using conventional free radical polymerization described here. The
coordination polymerization is used to obtain high molecular weight polypropyl-
ene (detailed in Chap. 9).

ROOR CH 2CHOR + RO (7.59)

CH 2CH Y

Y H2 C CHY CH2CH2 + H2C CY (7.60)

Y

H H
CH2C + CCl4 CH2CCl + CCl3
ð7:61Þ

H2C CH + CCl3 Cl3CCH2 CH etc .

ð7:62Þ

CH3 CH3
CH2CH + H3CHC CH2 CH2CH2 + CH2 CH CH2

ð7:63Þ

From the molecular weight control point of view, the chain transfer agent plays
the most effective way. For instance, a thiol compound has been used widely as
chain transfer agent due to its high affinity for hydrogen transfer as
160 7 Radical Chain Polymerization

CH2 CH + RSH CH2 CH2 + RS

ð7:64Þ
Y Y

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
Rp
mtr ¼ ð7:65Þ
Ri þ Rtr
Since transfer reactions are second order, with
Rtr ¼ ktr ½M½T ð7:66Þ
where T is the transfer agent, one can rewrite the expression for mtr , taking into
account all possible transfer reactions, as
kp ½M ½M kp ½ M 
mtr ¼ 2 P
¼ P ð7:67Þ
2kt ½M þ ktr ½M½T 2k t ½ M þ ktr ½T

It is known that
kp ½ M 
m¼
2kt ½M
One can write the reciprocal of Eq. 7.67 for mtr as
P
1 1 ktr ½T
¼ þ ð7:68Þ
mtr m kp ½ M 
The ratio of the transfer rate constant to that of propagation is commonly
defined as the chain transfer constant, CT , for a particular monomer:
ktr
¼ CT ð7:69Þ
kp
Substituting Eq. 7.69 into Eq. 7.68, one obtains
P
1 1 CT ½T
¼ þ ð7:70Þ
mtr m ½M 
As the rate of transfer and concentration of the transfer agent increase, the
kinetic chain length becomes progressively smaller. Chain transfer constants for a
number of compounds and monomers are available in the polymer literature,
several of which are given in Table 7.11.
7.5 Kinetics of Free Radical Chain Polymerization 161

Table 7.11 Representative chain transfer constants CT, propagation rate constants kp, and ter-
mination rate constants kt, for styrene and methyl methacrylate (reaction temperature 60°C) [3]
Transfer Agent CT 9 104
Styrene Methyl Methacrylate
Benzene 0.023 0.04
Toluene 0.125 0.20
Chloroform 0.5 1.77
Carbon tetrachloride 90 2.40
Carbon tetrabromide 22,000 2,700
1-Butanethiol 210,000 6,600
kp (L/mol-s) 176 515
kt 9 10-6 (L/mol-s) 73 25.5

When the concentration of transfer agent is high and ktr is much greater than kp ,
very low molecular weight polymers called telomers are obtained. The process is
called telomerization. Chain transfer reactions can also be used to prevent free
radical polymerizations. One type of compound, added as a stabilizer to vinyl
monomers, is an alkylated phenol 10, which can transfer its phenolic hydrogen to
form a new radical (Eq. 7.71) that undergoes coupling reaction (Eq. 7.72) rather
than initiating polymerization. Such compounds, called inhibitors, are commonly
added to monomers to prevent premature polymerization during shipment or
storage.

OH
R R
R' +

R
10
ð7:71Þ
O O O
R R R R R R
R'H +

R R R

OR' O O
R R R
R R R
R' R' +
+ ð7:72Þ

R R R R'
162 7 Radical Chain Polymerization

7.6 Living Polymerization

When the termination reaction is not present in the polymerization of monomers,

we call the polymerization is living polymerization. An important consequence of
living polymerization is that the average degree of polymerization is simply equal
to the ratio of the initial monomer concentration to the initiator concentration as
shown in Eq. 7.73. There are different approaches to achieve living radical
polymerizations which are discussed below.
½M0
DP ¼ ð7:73Þ
½I0

7.6.1 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) [6]. The lifetime in the conventional
radical polymerization is very short (in second) because of the presence of
bimolecular termination. 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 [3]. Living radical
polymerization (LRP) with reversible termination generally proceeds as follows:

R-Z R + Z (7.74)
Reactive Stable
radical radical

RM n Propagating radical (7.75)

Z

Bimolecular RMn - Z Dormant species (7.76)

termination

The initiator RZ undergoes homolytic bond breakage to produce one reactive

and one stable free radical (Eq. 7.74). The reactive radicals quickly initiate
polymerization (Eq. 7.75), but the stable radicals are too stable to initiate poly-
merization. However, the stable radicals preserve the propagation chain being
7.6 Living Polymerization 163

living without any termination (Eq. 7.76). For living polymerization, it is impor-
tant to have all the initiator decomposes at once so that all propagating radicals
grow almost at the same time. Fast initiation is important, but it is the fast equi-
librium between the propagating radical and dormant species with an appropriate
equilibrium constant that determines the living characteristics of polymerization.
The equilibrium constant must be low but not too low; that is, the concentration of
propagating radical must be sufficient to achieve a reasonable propagation rate but
not so high that normal bimolecular termination becomes important.
At the beginning of the reaction, the concentrations of propagating and stable
radicals are equal, but they change rapidly with the progress of reactions. The
concentrations of stable radicals are increasing while the concentrations of prop-
agating radicals are decreasing because the reactions are shifted toward more
stable species as shown in Eqs. 7.74 and 7.76. Overall, the concentration of stable
radicals is about four orders higher than that of propagating radicals. The con-
centration of propagating radicals is about the same or lower than the conventional
radical polymerization. The stable radicals function as controlling agent to form
reversible dormant species with propagating radicals. The equilibrium favors the
dormant species by several orders of magnitude as compared with the propagating
radicals. Thus, the concentration of dormant species is about six orders higher than
that of propagating radical. In short summary, the introduction of the dormant
species in the radical polymerization suppresses the bimolecular termination
reaction to have a living polymer. The average life time of the living polymer has
been increased by at least four orders of magnitude. Thus, the living free radical
polymerization becomes possible due to the formation of stable radicals and
reversible dormant species. By sequential living polymerization of one kind of
monomer to another kind of monomer, well-defined block copolymers can be
obtained through living polymerization. The second type of monomers usually has
to add quickly after the first kind monomers are consumed to avoid any bimo-
lecular reactions among propagating radicals. Currently, reversible termination
reactions and reversible chain transfer reactions are employed in the living free
radical polymerizations. They are discussed below.

7.6.2 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 [6]. For instance,
the polymerization of styrene using 1-chloro-1-phenylethane (11, or the bromo
analog) as initiator in the presence of a copper (I) bipyridyl (bpy) complex. Ini-
tiation occurs when a halogen atom is transferred from 11 to the complex
(Eq. 7.77). The resultant 1-phenylethyl radical in turn adds to a styrene molecule
(Eq. 7.78). The halogen atom is then reversibly transferred to the styryl radical
(Eq. 7.79), thus preventing radical termination reactions from occurring while
164 7 Radical Chain Polymerization

allowing the propagation reaction to proceed.

+ Cu(I)(bpy) CH 3 CH +
CH 3CHCl Cu(II)(bpy)Cl

ð7:77Þ

11

CH3CH + H2C CH CH3CHCH2CH

ð7:78Þ

CH3CHCH2CH + Cu(II)(bpy)Cl CH3CHCH2CHCl + Cu(I)(bpy)

ð7:79Þ

7.6.3 Nitroxide-Mediated Polymerization (NMP)

Stable nitroxide radical such as TEMPO 12 can mediate polymerization as shown

in Eq. 7.80. 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. Dissociation in turn
frees the chain end radical to add to other styrene molecules.

H3C CH3 H3C CH3

CH2CH + O N CH2CH O N
ð7:80Þ
H3C CH H3C CH
3 3

12

7.6.4 Radical Addition-Fragmentation Transfer (RAFT)

ATRP and NMP control chain growth by reversible termination. RAFT living
polymerizations control chain growth through reversible chain transfer. A chain-
7.6 Living Polymerization 165

transfer agent R’CSSR, such as cumyl dithiobenzoate 13 reversibly transfer a

labile end group (a dithioester end group) to a propagating chain (Eq. 7.81). The
polymerization is carried out with a conventional initiator such as a peroxide or
AIBN in the presence of the chain-transfer agent. The key that makes RAFT a
living polymerization is the choice of the RAFT transfer agent. Living polymer-
ization occurs with dithioesters because the transferred end group in the polymeric
dithioester is as labile as the dithioester group in R’CSSR. This results in an
equilibrium between dormant polymer chains and propagating radicals (Eq. 7.82
with K = 1), which controls the living polymerization.

CH3
S S
CH3
ðÞ
13
R' R' R'
Mn + + R (7.81)
S SR MnS SR MnS S

R' R' R'

Mm + + Mn ð7:82Þ
S SMn MmS SMn MmS S

RAFT works with a wider range of monomers than TEMPO and ATRP. RAFT
does not produce polymers with metal catalysts but produce polymers with di-
thioester group with odors and colors. The design and synthesis of RAFT agent has
been thoroughly reviewed and outlined. The methods are extended to functional
RAFT agent and macro-RAFT agent [7].
The limitations of living radical polymerization are that irreversible bimolec-
ular termination of propagating radicals will occur at high monomer conversion,
polyfunctional initiators, high initiator concentration, and high target molecular
weight ([100,000).

7.7 Polymerization of Dienes

Polymerization of isolated dienes leads to crosslinked polymers when the double

bonds react independently of each other. In certain cases, the addition reactions
can occur within the double bonds of molecule and lead to cyclic polymers.
Polymerization of divinylformal 14 illustrates this process as shown in Eq. 7.83.
166 7 Radical Chain Polymerization

R R
R +
O O O O O O
14

R
O O

ð7:83Þ

The normal (head-to-tail) mode of addition yields the six-membered ring,

whereas abnormal (head-to-head) addition (Eq. 7.84) gives the five-membered
ring. The former is preferred, but both are formed in significant amounts.

R R
ð7:84Þ
O O O O

Several diallyl monomers such as 15 and 16 are used commercially to prepare

highly cross-linked thermosetting allyl resins or for crosslinking other polymers.
Diallyl phthalate 15 is used widely in the manufacturing of printed wiring boards,
electrical insulations, fiber reinforced composites, etc. Diethylene glycol bis (allyl
carbonate) 16 is used to make optical clear polymers for the applications in eye-
wares, lenses, camera filters, panel covers, and the like.
O
O O
O O
O
O 2
O 16
15
Conjugated dienes such as 1,3-butadiene 17 undergo both 1,2- and 1,4-addition
to obtain polymers through the delocalized radical intermediate 18 (Eq. 7.85).
Thus 1,2-addition gives polymer 19 with pendant vinyl groups, while 1,4-addition
leads to polymer with unsaturation in the chain. In the latter case, both cis 20 and
trans 21 configurations are possible.
7.7 Polymerization of Dienes 167

R
CH2 CH CH CH2 R CH2 CH CH CH2
17 18

CH 2CH CH 2 CH2 CH2 H ð7:85Þ

CH CH2 H H H CH2
19 20 21

With substituted dienes like isoprene (2-methyl-1,3-butadiene) the situation is

more complicated; 1,2 and 3,4 structures (22 and 23, respectively) as well as cis-
and trans-1,4 (24 and 25), are possible. All are formed in free radical polymeri-
zation but as expected the head-to-tailtrans-1,4 25 predominates. Natural Hevea
rubber contains the head-to-tail of 1,4-polyisoprene units with cis structure 24.
CH3
CH2CH
CH 2C
C CH2
CH CH2 CH3
22 23

CH2 CH2 CH2 H

CH3 H CH3 CH2

24 25
Table 7.12 lists the percentages of each structural unit at different polymeri-
zation temperatures for the three most important diene monomers—butadiene,
isoprene, and chloroprene (2-chloro-1,3-butadiene). It is interesting to note that,
for isoprene, the amount of cis-1,4 structure increases with increasing temperature
up to about 100 °C, then it decreases. The total amount of 1,2 and 3,4 polymer
(approximately 10 %) does not change appreciably with temperature; however, the
3,4 structure is favored at higher temperatures. With chloroprene, the trans-1,4
structure also decreases with increasing temperature, but the amount of trans-1,4 is
slightly higher than that of isoprene over the temperature range measured. The
results may be from the larger size of Cl group than that of CH3 group, a steric
hinderance dominated factor.
168 7 Radical Chain Polymerization

Table 7.12 Compositions of free radical-initiated diene polymers [2]

Monomer Polymerization Percent
temperature(°C)
cis-1,4 trans-1,4 1,2 3,4
Butadiene -20 6 77 17 –
20 22 58 20 –
100 28 51 21 –
233 43 39 18 –
Isoprene -20 1 90 5 4
-5 7 82 5 5
50 18 72 5 5
100 23 66 5 6
257 12 77 2 9
Chloroprene -46 5 94 1 0.3
46 10 81–86 2 1
100 13 71 2.4 2.4

7.8 Temperature Effect of the Free Radical Polymerization

By varying the polymerization temperature, there is big effect on the rate and
degree of polymerization [3]. When the temperature increases, the rate of poly-
merization increases, but the degree of polymerization decreases as shown in
Fig. 7.2. The quantitative effect of temperature is complicated and is discussed in
the following sections.

Fig. 7.2 Dependence of the

polymerization rate (s) and
polymer molecular weight 20.0 20.0
Weight-average molecular weight, M w x 10-6

(h) on the temperature for

10.0 10.0
Rate of polymerization, % / hour

the thermal self-initiated

polymerization of styrene [3]
5.0 5.0

2.0 2.0

1.0 1.0

0.5 0.5

0.2 0.2

0.1 0.1

0. 05 0.05

2.3 2.5 2.7 2.9 3.1

1
X10 3(1/K)
T
7.8 Temperature Effect 169

7.8.1 Activation Energy and Frequency Factor

The quantitative effect of temperature on rate of polymerization (Rp ) and degree of

polymerization (X n Þ is very complex since they depend on a combination of three
rate constants of initiation (kd Þ, propagation (kp Þ and termination (kt Þ. Each of the
rate constants can be expressed by an Arrhenius equation

k ¼ AeE=RT ð7:86Þ
or
E
ln k ¼ ln A  ð7:87Þ
RT
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. Table 7.13 shows the values of
the frequency factor and activation energy of propagation (Ep ) and termination (Et )
of several monomers.
The variations in the values of the frequency factor of propagation (Ap ) are
greater than those in Ep which indicates that steric effects are probably the more
important factor to determine the absolute value of kp . Thus, the more hindered
monomers such as methyl methacrylate have lower kp and Ap values than the less
hindered ones such as methyl acrylate. The Ap values in general are lower than the
usual value (1011–1013) of the frequency factor of a bimolecular reaction. The
result is probably due to a large decrease in entropy on polymerization. The
variations in the values of the frequency factor of termination (At ), generally
follow the trend of Ap values, but with larger values.

Table 7.13 Kinetic parameters in radical chain polymerizationa [3]

Monomer Ep Ap 9 10-7 Et At 9 10-9
1,3-Butadiene 24.3 12 – –
2-Vinylpyridine 33 – 21 –
Acrylonitrile 16.2 – 15.5 –
Ethylene 18.4 – 1.3 –
Methyl acrylate 29.7 10 22.2 15
Methyl methacrylate 26.4 0.087 11.9 0.11
Styrene 26 0.45 8.0 0.058
Vinyl acetate 18 3.2 21.9 3.7
Vinyl chloride (50°C) 16 0.33 17.6 600
Tetrafluoroethylene(83°C) 17.4 – – –
a
Ep values are in kJ/mole of polymerizing monomer; Et values are in kJ/mole of propagating
radicals; Ap and At values are in liters/mole-second. The data are obtained at 60°C unless
otherwise noted
170 7 Radical Chain Polymerization

7.8.2 Rate of Polymerization

For a polymerization initiated by the thermal decomposition of an initiator, the

polymerization rate depends on the ratio of three rate constants kp ðkd =kt Þ1=2
according to Eq. 7.53. The temperature dependence of this ratio can be obtained
by combining three separate Arrhenius equations as below
  1=2    1=2     
kd Ad ½Ep þ E2d  E2t 
ln kp ¼ ln Ap  ð7:88Þ
kt At RT
The overall activation energy of rate of polymerization ER is equal to
Ep þ ðEd =2Þ  ðEt =2Þ. From Eq. 7.53, one can rewrite the above equation as
  1=2  h i E
Ad 1 R
ln Rp ¼ ln Ap þ ln ðf ½I Þ2 ½M   ð7:89Þ
At RT

By plotting ln Rp versus 1/T, one can obtain ER and Ap ðAd =At Þ1=2 from the slope
and intercept, respectively.
Table 7.14 shows the thermal properties of commonly used initiators. The
activation energy of initiator decomposition is in the range of 120–150 kJ mole-1
in general. The Ep and Et value of most monomers are in the ranges of 20–40 kJ
mole-1 and 8–20 kJ mole-1 respectively (Table 7.13). Thus the ER of most
polymerization initiated by thermal initiator decomposition is about 80–90 kJ
mole-1. This corresponds to a two to three time rate increase for every 10°C
temperature increase. The situation is different for other mode of initiation. The
redox initiation (e.g., Fe2+ with thiosulfate or cumene hydroperoxide) usually takes
place at lower temperature as compared to the thermal polymerizations because
the former has lower activation energy. The Ed value of redox initiation is only
about 40–60 kJ mole-1 or about 80 kJ mole-1 less than that of thermal initiation.
This leads to an ER redox polymerization about 40 kJ mole-1 or about half of the
nonredox initiators.
The initiation step of photo polymerization is temperature independent
(Ed ¼ 0), because the decomposition of initiator is induced by light rather than by

Table 7.14 Properties of common thermal initiatorsa,b [3]

Initiator kd 9 105 T (°C) Ed
0
2,2 -Azobisisobutyronitrile 0.845 60 123.4
Acetyl peroxide 2.39 70 136.0
Benzoyl peroxide 5.50 85 124.3
Cumyl peroxide 1.56 115 170.3
t-Butyl peroxide 3.00 130 146.9
t-Butyl hydroperoxide 0.429 155 170.7
a
All data are for decompositions in benzene solution
b
The units of kd are s-1 ; the units of Ed are kJ/mole
7.8 Temperature Effect 171

heat. The overall activation energy of photo polymerization is then only about
20 kJ mole-1 which indicates this polymerization is relatively insensitive to
temperature. However, most photo initiators can also be decomposed thermally;
the initiators may undergo appreciable thermal decomposition in addition to photo
decomposition at higher temperatures. In such cases, one must take into account
both the thermal and photo initiations. The initiation and overall activation ener-
gies for a purely thermal self-initiated polymerization are approximately the same
as for initiation by the thermal decomposition of an initiator. For the thermal, self-
initiated polymerization of styrene, its Ed is 121 kJ mole-1 and ER is 86 kJ
mole-1. However, pure thermal polymerization proceeds at very slow rates
because of very low frequency factor (104–106) resulting in very low probability of
initiation process.

7.8.3 Degree of Polymerization

The effect of temperature on the molecular weight of the polymer produced by

thermally initiated polymerization will be determined by the ratio of kp =ðkd =kt Þ1=2
according to Eq. 7.56 of the degree of polymerization, if transfer reactions are
negligible. The variation of the ratio with temperature can be expressed by
       
kp Ap Ep  E2d  E2t
ln ¼ ln  ð7:90Þ
ðkd kt Þ1=2 ðAd At Þ1=2 RT

The overall activation energy of degree of polymerization (EX n Þ is equal to

Ep  ðEd =2Þ  ðEt =2Þ . Then the temperature effect on the degree of polymeri-
zation can be expressed by
   
Ap ½M E
lnX n ¼ ln 1=2
þ ln 1=2
 Xn ð7:91Þ
ðAd At Þ ðf ½IÞ RT

EX n has a value of about -60 kJ mole-1 and X n decreases rapidly with

increasing temperature. EX n is about the same for a purely thermal, self-initiated
polymerization (Fig. 7.2). For a pure photo polymerization, EXn is positive by
approximately 20 kJ mole-1, since Ed is zero, and X n increases moderately with
temperature. For all other cases, X n decreases with temperature.
When chain transfer occurs in the polymerization, the temperature effect on the
X n depends on the relative importance of the chain transfer reaction. For the case
where chain transfer to chain transfer agent T, one can obtain the following
equation according to Eq. 7.70.
172 7 Radical Chain Polymerization

Table 7.15 Activation parameters for chain transfer in styrene polymerization (60°C) [3]
Transfer agent -(Ep-Etr,S) log(Atr,S/Ap)
Benzene 62.0 3.9
Carbon tetrachloride 20.9 1
Cyclohexane 56.1 3.1
Ethyl benzene 23.0 -0.55
Isopropyl benzene 23.0 -0.47
n-Butyl bromide 46.1 2
n-Butyl chloride 58.6 4
n-Butyl iodide 29.3 1
t-Butyl benzene 57.4 3.8
Toluene 42.3 1.7

" !#
½M  1 1 kp Ap ðEp  Etr Þ
 ln   ¼ ln ¼ ln  ð7:92Þ
½T  X n Xn 0 ktr Atr RT

Now, EX n is equal to (Ep  Etr ) and can be obtained by plotting the left side of
equation versus 1/T. The (Ep  Etr ) is usually in the range of -20 to -65 kJ
more-1 and the molecular weight decreases with increasing temperature.
Table 7.15 shows the activation parameters for chain transfer in styrene poly-
merization using different chain transfer agents. The frequency factors for transfer
reactions are usually greater than those of propagations.

7.9 Thermodynamics of Free Radical Polymerization

The thermodynamics of free radical polymerization [3] can be expressed by

DGp = DHp-TDSp. The DGp, DHp, and DSp for a polymerization are the differ-
ence in free energy, enthalpy, and entropy, respectively, between 1 mol of
monomer and 1 mol of repeating units in the polymer product. The thermody-
namic 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 (DHp is ‘‘negative’’) and
exoentropic (DSp is ‘‘negative’’). The exothermic nature of polymerization arises
because the process involves the exothermic conversion of p-bonds (less stable) in
monomer molecules into r-bond (more stable) in the polymer. The negative DSp
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. Table 7.16 shows the wide
range of DHp values for various monomers and also shows the general thermo-
dynamic feasibility for any carbon–carbon double bond (DGp is negative). How-
ever, thermodynamic feasibility does not indicate the experimental conditions of
7.9 Thermodynamics of Free Radical Polymerization 173

Table 7.16 Enthalpy and entropy of polymerization at 25 °C[3]

Monomer -4H -4S
Ethylene 93 155
Propene 84 116
1-Butene 83.5 113
Isobutylene 48 121
1,3-Butadiene 73 89
Isoprene 75 101
Styrene 73 104
a-Methylstyrene 35 110
Vinyl chloride 72 –
Vinylidene chloride 73 89
Tetrafluoro ethylene 163 112
Acrylic acid 67 –
Acrylonitrile 76.5 109
Maleic anhydride 59 –
Vinyl acetate 88 110
Methyl acrylate 78 –
Methyl methacrylate 56 117
4H refer to the conversion of liquid monomer to amorphous or (slightly) crystalline polymer.
4S refers to the conversion of monomer (at a concentration of 1 M) to amorphous or slightly
crystalline polymer. The subscripts lc are often used with 4H and 4S to show the initial and final
states (that is, 4Hlc and 4Slc). The units of 4H are kJ/mole of polymerized monomer; the units
of 4S are J/K-mole

polymerization. The DSp values fall in a narrower range of values. DSp is in a small
range *100 to *150 J/K-mol and DGp is ‘‘negative’’ due to –TDSp over weight
DHp. Thus, polymerization is a favored reaction from thermodynamic point of
view.

7.9.1 Monomer Reactivity

Although the polymerization reaction is thermodynamically favored, the kinetic

feasibility of polymerization varies considerably from one monomer to another
depending on the stability of monomer radical and polymer radical [3].
As shown in Table 7.16, the DH values for ethylene, propene, and 1-butene are
very close to the difference (82–90 kJ/mole) between the bond energies of the p-
bond in an alkene and the r-bond in an alkane. The DH values for the other
monomers vary considerably. The variations in DH for differently substituted
ethylenes arise from any of the following effects: (1) differences in the resonance
stabilization of monomer and polymer due to differences in conjugation or
hyperconjugation, (2) steric strain differences in the monomer and polymer arising
174 7 Radical Chain Polymerization

from bond angle deformation, bond stretching, or interactions between nonbonded

atoms, and (3) differences in hydrogen bonding or dipole interactions in the
monomer and polymer. The following monomers (I) can be stabilized through
resonance that decreases DH of polymerization. However, the monomer (II) is
poorly conjugated and its DH is similar to that of ethylene.

Type I Monomer
H2C CH

CH3
H2C C

CH 2 CH CH CH2
H 2C C CH3

CH3
O
H 2C C C O(H or CH3)
CH3
H2C CH

CN
Type II Monomer
O
CH2 CH O C CH3

Many substituents stabilize the monomer but have no appreciable effect on

polymer stability, since resonance is only possible with the former. The net effect
is to decrease the exothermicity of the polymerization. Thus, hyperconjugation of
alkyl groups with the C=C lowers DH for propylene and 1-butene polymerizations.
Conjugation of the C=C with substituents such as the benzene ring (styrene and a-
methylstyrene), and alkene double bond (butadiene and isoprene), the carbonyl
linkage (acrylic acid, methyl acrylate, methyl methacrylate), and the nitrile group
(acrylonitrile) similarly leads to stabilization of the monomer and decreases
enthalpies of polymerization. When the substituent is poorly conjugating as in
vinyl acetate, the DH is close to the value for ethylene.
The effect of 1,1-disubstitution manifests itself by decreased DH values [3].
This is a consequence of steric strain in the polymer due to interactions between
substituents on alternating carbon atoms of the polymer chain. In 25, the polymer
chain is drawn in the plane of the text with the H and Y substituents placed above
7.9 Thermodynamics of Free Radical Polymerization 175

and below the plane of the text. The dotted and triangular lines indicate substit-
uents below and above this plane, respectively. Such interactions are referred to as
1,3-interactions and are responsible for the decreased DH values in monomers such
as isobutylene, a-methyl styrene, methyl methacrylate, and vinyl chloride. The
effect in a-methyl styrene is especially significant. The DH value of -35 kJ/mole
is the smallest heat of polymerization of any monomer. To summarize, the stability
of the polymer radical is more important than the stability of the monomer toward
addition of a free radical in the propagation reactions.

H H H H H H

Y Y Y Y Y Y

1,3-Interaction in polymer
25

7.9.2 Ceiling Temperature

The reversibility of vinyl polymerization reactions has been observed which

depends on the monomer reactivity and the stability of polymer radical as shown
in the following:
kp
Mx  þM  Mðxþ1Þ  ð7:93Þ
kdp

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 DG of polymerization is zero, or

Table 7.17 Representative Monomer Tc (°C)

ceiling temperatures, Tc, of
pure liquid monomers [3] 1,3-Butadiene 585
Ethylene 610
Isobutylene 175
Isoprene 466
Methyl methacrylate 198
a-Methyl styrene 66
Styrene 395
Tetrafluoro ethylene 1,100
176 7 Radical Chain Polymerization

DH
Tc ¼ ð7:94Þ
DS
It follows that whatever affects DH or DS for a given monomer (e.g., monomer
concentration, pressure) will also affect Tc. Table 7.17 lists ceiling temperatures
for several pure liquid monomers.

7.9.3 Characteristics of DS Values of Free Radical

Polymerization

While the DH values vary over a wide range for different monomers, the DS values
are less sensitive to monomer structure, being relatively constant within the range
of *100–120 J/K-mole. The TDS contribution to the DG of polymerization will
be small and will vary only within a narrow range. Thus, the variation in the
TDS term at 50°C for all monomers is in the narrow range of 30–40 kJ/mole. The
DS of polymerization arises primarily from the loss of the translation entropy of
the monomer. Losses in the rotational and vibration entropies of the monomers are
essentially balanced by gains in the rotation and vibration entropies of the poly-
mer. Thus, DS for polymerization is essentially the translational entropy of the
monomer, which is relatively insensitive to the structure of the monomer.

7.10 Molecular Weight Distribution at Low Conversion

The molecular weight of radical chain polymerization is complicated because

several possible terminations–disproportions, coupling, and various transfer
reactions are involved. Molecular weight changes with % conversion, due to the
changes in the concentrations of monomer and catalyst, and the rate constant of
propagation and termination.
At low conversion where all of the kinetic parameters (½M ; ½I ; kd ; kp ; kt ) are
approximately constant. Under these conditions, the polymer molecular weight
does not change with conversion. The molecular weight distributions can be
derived as did in the step polymerization and are shown in Eqs. 7.95, 7.96, 7.97,
7.98, 7.99, and 7.100 as the number-fraction, number-, and weight-fraction dis-
tributions, the number- and weight-average degrees of polymerization, and the
breadth of the distribution, respectively.

N x ¼ px1 ð1  pÞ ð7:95Þ

Nx ¼ N0 ð1  pÞ2 px1 ð7:96Þ

Wx ¼ xð1  pÞ2 px1 ð7:97Þ

7.10 Molecular Weight Distribution at Low Conversion 177

1
Xn ¼ ð7:98Þ
ð1  pÞ

ð1 þ pÞ
Xw ¼ ð7:99Þ
ð1  pÞ

Xw
¼1þp ð7:100Þ
Xn
Disproportional or chain transfer or a combination of two: one polymer mol-
ecule is produced from each kinetic chain. When p is used as the probability to
continue propagation, the molecular weight distribution can be shown in the
following.
p ¼ Rp =ðRp þ Rt þ Rtr Þ ð7:101Þ
where Rp, Rt, and Rtr are the rates of propagation, termination by disproportion-
ation, and chain transfer, respectively. The breadth of the size distribution X w =X n
is equal to 2 as p approaches unity. For termination by coupling (Rtr ¼ 0 and Rt is
the rate of coupling), a polymer arises from the combination of two kinetic chains,
the size distribution is narrow.
Consider the probability N YþZ of formation of an x-sized polymer by the
coupling of y- and z-sized propagating radicals. N YþZ is the product of the prob-
abilities, N Y and N Z , of forming the y- and z-sized propagating radicals.
According to Eq. 7.95, N Y and N Z are given in the following:

N Y ¼ ð1  pÞpy1 ð7:102Þ

N Z ¼ ð1  pÞpz1 ð7:103Þ

*y þ z ¼ x

) N Z ¼ ð1  pÞpxy1 ð7:104Þ

Then N yþZ ¼ ð1  pÞ2 px2 ð7:105Þ

Equation 7.105 gives the probability of forming an x-sized polymer molecule

by only one of many equally probable pathways. There are (x-1) possible path-
ways of producing an x-sized polymer molecule when x is an even number. Each
of the pathways has the same probability. Therefore, the total probability N x of
forming an x-sized polymer molecule is given by

N x ¼ ðx  1Þð1  pÞ2 px2 ð7:106Þ

where N x is mole or number-fraction distribution.
When x is an odd number there are x pathways
178 7 Radical Chain Polymerization

N x ¼ xð1  pÞ2 px2 ð7:107Þ

For polymerization yielding in high polymer, the difference between x and
(x ? 1) is negligible and can be ignored. Then, we can have the following
relationship:
1
Wx ¼ xð1  pÞ3 ðx  1Þpx2 ð7:108Þ
2
X n ¼ 2=ð1  pÞ ð7:109Þ

X w ¼ ð2 þ pÞ=ð1  pÞ ð7:110Þ

Xw
¼ ð2 þ pÞ=2 ð7:111Þ
Xn
At high conversion, the size distributions become much broader than those
described above for low concentration case. Kinetic chain length m is defined
below:

m ¼ kp ½M =2ðfkd kt ½I Þ1=2 ð7:56Þ

then,
1
m / ½M=½I 2 ð7:112Þ
The molecular weight is increased according to Eq. 7.56. Because ½I is
decreased faster than ½M, then the molecular weight of polymer is increased with
% conversion. For polymer having practical usage, we want its PDI as narrow as
possible. Sometimes, it is necessary to have multiple addition of initiator,
monomer during the polymerization to minimize the molecular weight broadening.
For auto-acceleration, the PDI is even larger with a value of 5–10. For chain
transfer branch polymer, is also large with a PDI of 20–50, because chain transfer
to polymer increases as the polymer size increases.

7.11 Synthesis of Commercial Polymers

The synthesis of some common polymers in the industrial scale is discussed below.

7.11.1 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. Batch
7.11 Synthesis of Commercial Polymers 179

processes are not useful since the long residence time gives relatively poor control
of product properties. Long-chain branching due to intermolecular chain transfer
becomes excessive with deleterious effects on the physical properties. Continuous
processes allow better control of the polymerization.
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.
Low-density polyethylene 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).
Low-density polyethylene (LDPE) has a wide range and combination of
desirable properties. Its very low Tg of about -120°C and moderately crystallinity
and Tm of 105–110°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, with X w =X n in the range of 3–20.
Film application accounts for over 60 % of polyethylene consumption. Injec-
tion molding of toys, housewares, paint-can lids, and containers accounts for
another 10–15 %. About 5 % of the LDPE produced is used as electrical wire and
cable insulation. Extrusion coating of paper to produce milk, juice, and other food
cartons and multiwall bags accounts for another 10 %. Trade names for polyeth-
ylene include marlex, nipolon, etc.

7.11.2 Polystyrene

Continuous solution polymerization is the most important method for the com-
mercial production of polystyrene although suspension polymerization is also
used. Emulsion polymerization is important for the synthesis of copolymer of
acrylonitrile butadiene styrene(ABS). Commercial polystyrene (PS) has number-
average molecular weights in the range of 50,000–150,000 with X w =X n values of
2–4. Although completely amorphous (Tg = 85 °C), its bulky rigid chains (due to
phenyl–phenyl interactions) impart good strength with high-dimensional stability
(only 1–3 % elongation); PS is a typical rigid plastic. Expandable polystyrene,
either crystal polystyrene or styrene copolymers impregnated with a blowing
agent, e.g., pentane, is used to produce various foam products such as disposable
drinking cap, egg cartons, etc.
180 7 Radical Chain Polymerization

7.11.3 Polyvinyl Chloride

Most poly(vinyl chloride) (PVC) is commercially produced by suspension poly-

merization. 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°C, 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. Tough and rigid PVC became flexible by using plasticizers
(e.g., di-i-octylphthalate, tritolyl phosphate, epoxidized oils). Rigid pipe is used for
home and construction, vinyl siding, window frames, rain-gutter, packaging, and
gloves.

7.11.4 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°C which is not very useful, but widely used in water based paints,
adhesives for papers, textiles, and wood. PVAC is also used for producing poly-
vinylalcohol (PVA) by hydrolysis that is used as thickening agents, coatings, and
adhesives.

7.11.5 Polyvinylidene Chloride

Polyvinylidene chloride (–CH2–CCl2–)n and its copolymer with vinyl chloride,

acrylonitrile, and acrylates, usually prepared by suspension or emulsion poly-
merization. They are useful as oil, fat, oxygen and moisture-resistant packaging
films (Saran wrap), container, coatings, tank liners, and monofilaments in drapery
fabrics and industrial filter cloths.

7.11.6 Acryl Polymer

Poly(methyl methacrylate) (PMMA) can be polymerized by bulk, solution, sus-

pension, and emulsion processes. PMMA is completely amorphous but has high
strength and excellent dimensional stability due to the rigid polymer chains
(Tg = 105°C). Polyacrylates differ considerably from the polymethacrylates. They
are softer since the polymer chains are not nearly as rigid [e.g., poly(ethyl acrylate)
(PEA), Tg = -24°C], due to the absence of the methyl groups on alternating
carbons of the polymer chains.
7.11 Synthesis of Commercial Polymers 181

Various rigid PMMA products, such as sheet, rod, and tube, are produced by
bulk polymerization in a casting process. Polymerization is carried out in stages to
allow easier dissipation of heat and control of product dimensions since there is a
very large (21 %) volume contraction on polymerization. Partially polymerized
monomer like syrup (about 20 % conversion) is produced by heating for about
10 min at 90°C with a peroxide. The syrup is cooled to ambient temperature and
poured into a mold, and then the assembly is heated in a water or air bath to
progressively higher temperatures. The maximum temperature used is 90 °C, since
higher temperatures can lead to bubble formation in the product as the boiling
point of methyl methacrylate is 100.5°C. Trade name for acrylate and methacrylate
polymer products includes Acrylite, Plexiglas, Lucite, etc.
In commercial production, polyacrylonitrile ([–C–C(CN)–]n) (PAN) is syn-
thesized by either solution or suspension polymerization. Polyacrylonitrile con-
tains polar group to have high secondary force, so it exhibits good fiber property.
PAN is a source of carbon fiber which is produced by cyclization of polymer at
2,000 °C or above.
From the viewpoint of sales volume, all other members of the acrylic family
constitute a small fraction of the total. However, many of them are useful specialty
products. Polyacrylamide, poly(acrylic acid), and poly(methacrylic acid) and some
of their copolymers are used in various applications that take advantage of their
solubility in water. Poly(acrylic acid) and poly(methacrylic acid) are used as
thickening agents, adhesives, dispersants for inorganic pigments in paints, flocc-
ulants, and crosslinked ion-exchange resins.

7.11.7 Fluoropolymers

The fluoropolymers are obtained mainly by suspension polymerization; emulsion

polymerization is also practiced. 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 pre-
cipitation of growing radicals (leading to greatly decreased termination). Fluoro-
polymers can withstand a wide variety of chemical environments and are useful at
temperatures as low as -200°C and as high as 260°C. The various copolymers of
tetrafluoro ethylene and the other fluoropolymers, possessing lower Tm and crys-
tallinity, were developed to overcome the lack of melt processability of PTFE. A
true melt processable PTFE has been developed by blending two different
molecular weight polymers [8]. They are DuPont Zonyl MP 1000 and Zonyl MP
1,500 J at a specific mixing window of weight ratio of 40/60 and 20/80, respec-
tively. The PVDF exhibits novel piezoelectric properties which are useful for the
applications of actuators, artificial arms/legs, and so on.
182 7 Radical Chain Polymerization

7.11.8 Cost of Common Polymers

The cost of common polymers depends on the ease of synthesis and raw material
cost. Fluoropolymer is usually a high cost polymer compared to other polymers.
The cost comparison is in the increasing order of PE*PS \ phenolic alkyds
\ PMMA \ Nylon \ PTFE. The raw materials used for polymer synthesis are
derived from petroleum, with the increase in petroleum price and possible
depletion someday. Raw materials obtained from renewable source such as plants
or biomolecules are currently under intensive development. For instance, poly-
lactic acid can be obtained from bacterial fermentation of corn starch. It is bio-
degradable and has been used in disposable cups and plates.

7.12 Problems

1. Polymers can be synthesized via free radical polymerization among monomers

of ethylene, monosubstituted ethylene, 1,1-disubstituted ethylene. However,
polymers are difficult to obtain from 1,2-disubstitute ethylene by free radical
polymerization. Please explain.
2. Please show how degree of polymerization depends on temperature in (a)
polymerization initiated by thermal decomposition of an initiator, (b) photo-
polymerization (i.e., without initiator), and (c) without transfer reactions to
control molecular weight.
3. Please derive kinetic equations for radical chain polymerization in the pres-
ence of an inhibitor such that, essentially, all the chains are terminated by
reaction with the inhibitor. Show how the rate of polymerization depends on
the concentrations of monomer, initiator, and inhibitor at the steady state.
4. Please write the possible reaction products of two thermal initiators: diacetyl
peroxide, di-t-butyl peroxide, respectively.
5. In normal free radical processes with added initiator, the polymerization rate
and DP are proportional to the first power of monomer concentration. What
would be the effect of monomer concentration on DP in the thermal poly-
merization of styrene? Derive a kinetics expression to support your conclu-
sion. (Reminder: Initiation involves two monomer molecules.)
6. If equal concentrations of acrylonitrile (kp = 1,960 L/mol-s, kt = 782 9 10-6
L/mol-s) and methyl methacrylate (kp = 515 L/mol-s, kt = 25.5 9 10-6 L/
mol-s) were each polymerized at 60°C with equal concentrations of the same
initiators, which polymer would have the higher DP and by how much?
Assume polyacrylonitrile undergoes termination only by radical combination
and PMMA by disproportionation. Which polymer would have the higher M  n,
and by how much?
7. A certain monomer is polymerized by benzoyl peroxide labeled in the benzene
ring with carbon-14. (a) Analysis by carbon counting shows that the polymer
7.12 Problems 183

contains an average of 1.27 labeled phenyl groups per molecule. Assuming no

chain transfer occurred, what does this indicate about the mechanism of ter-
mination? (b) Vigorous basic hydrolysis removed 60 % of the carbon-14.
What does this indicate about the mechanism of initiation?
8. Predict the order of polymer molecular weight obtainable (highest to lowest)
by the free radical solution polymerization of styrene in benzene, toluene,
ethyl benzene, t-butyl benzene, and isopropyl benzene.
9. Poly(vinyl acetate) of number-average molecular weight 100,000 is hydro-
lyzed to poly(vinyl alcohol). Oxidation of the latter with periodic acid to
cleave 1,2-diol linkages yield a poly(vinyl alcohol) with degree of polymer-
ization of 200. Calculate the percentages of head-to-tail and head-to-head
linkages in the poly(vinyl acetate).
10. The living character of living radical polymerization is limited under certain
conditions, such as high monomer conversion, high initiator concentration,
and high targeted molecular weight([100,000). Please explain why these
conditions result in broadening of PDI and some difficulties in producing
block copolymers with well-defined block lengths of the different monomers.

References

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3. G. Odian, Principles of Polymerization, 4th edn (John Wiley & Sons, Inc. 2004)
4. F.W. Billmeyer Jr, Textbook of Polymer Science (John Wiley & Sons, Inc., New York, 1984)
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Industrial Training Associates Limited, London, 1984)
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