Chapter 8

lonic Chain Polymerization

8.1 Introduction

Besides free radical

mechanisms, discussed in Chapter 6, there are several other
mechanisms by which chain or addition
polymerization can take place. Prominent
among these are ionic mechanisms in which the
growing
chain end carbon bears
a
negative charge (carbanion) or a positive charge (carbonium ion). In the former
case, the
polymerization is known anionic polymerization
as and in the latter case
as cationic polymerization.
lonic polymerization can, in
general, be initiated by acidic or basic com-
pounds. For cationic polymerization, complexes of BF3, AlCl3, TiCl4, and SnCl4
with water, or alcohols, or
tertiary oxonium salts are particularly active initiators,
the positive ions in them causing chain initiation. One
can also initiate cationic
polymerization with HCI, H2S04, and KHSO4. Important initiators for anionic
polymerization are alkali metals and their organic compounds, such as phenyl-
lithium, butyllithium, phenyl sodium, sodium naphthalene, and
potassium.
triphenyl methyl
Several distinctive features of ionic chain
polymerization will now be high-
lighted. Ionic polymerizations are largely selective (as not all olefinic monomers
can undergo anionic and/or cationic
polymerization) and require stringent reaction
conditions including high monomer purity, whereas most olefinic
monomers un
dergo free radical polymerization under much less
stringent conditions. Cationic
polymerization is essentially limited to those monomers with electron-releasing
substituents and anionic polymerization to those
possessing electron-withdrawing
groups. Also, unlike in free-radical polymerizations where the characteristics of
the active centers
depend only on the nature of the monomer and are generally
independent of the reaction medium, in ionic polymerizations the
polarity of the
475
 476
Chapter8

solvent strongly influences the mechanism and rate of ionic polymerization. This
can be visualized as follows.
lonic polymerizations, shall sce later, involve successive insertion of
as we
monomer molecules between
an ionic chain end
(positive in cationic and negative
in anionic
polymerization) and a counterion of opposite charge. The macroion
and the counterion form an
organic salt which may, however, exist in several
forms depending on the nature and
degree of interaction between the cation and
anion of the salt and the reaction medium
(solvent/monomer). Considering, for
example, an organic salt A*B, a continuous spectrum of ionicities ("Winstein
spectrum) can be depicted as
AB A*B A /B
Covalent Contact
A* IIB A* + B
Solvent Solvated Free solvated
bonding (tight) separated (loose) ions
ion pair ion pair ion pair
(II) () (TV) (V) (8.1)
A range of behavior from
extreme of a completely covalent
one
other of completely free (and species (1) to thhe
highly solvated) ions (V) can be expected, including
the intermediate
species of tight or contact ion pair (II) and the solvent-separated
or loose ion
pair (). The contact ion pair always has a counterion (or gegenion)
of opposite charge close to the
propagating center and unseparated by solvent,
while the solvent-separated ion
pair involves ions that are partially separated by
solvent molecules.
Ionic polymerizations commonly involve two
types of propagating species
an ion pair (l1-IV) and a free ion
(V)-coexisting in equilibrium with each other.
The relative concentrations of these two
types of species, as also the identity of the
ion pair (that is, whether of type I, I, or IV),
depend on the particular reaction
conditions and especially the solvent or reaction medium, which has a
in ionic polymerizations. Loose ion pairs are more reactive than
large effect
while free ions are significantly more reactive than ion
tight ion pairs,
pairs. In general, more
polar media favor solvent-separated ion pairs or free solvated ions. In
hydrocarbon
media, free solvated ions do not exist, though other equilibria may occur between
ionpairs and clusters of ions (Rudin, 1982).
Solvents of high polarity are desirable for solvation of ions. However
cannot be employed for ionic
they
polymerizations. Thus highly polar hydroxylicsol
vents, such as water and alcohols, react with and destroy most ionic initiators
and propagating species. Other polar solvents such as ketones form highly stable
complexes with initiators, thus preventing initiation reactions. Most ionic poly-
merizations are, therefore, carried out in low or
moderately polar solvents such as
methyl chloride, ethylene dichloride, and pentane.
Though resembling free-radical chain polymerization in terms of initiation,
propagation, transfer, and termination steps, ionic polymerizations have signif-
 icantly different reaction kinetics and rates of ionic
polymerization are and
large much faster than in free-radical processes. This is mainly becauseby
nation by mutual destruction of active termi-
centers, which is prevalent in free-radical
systems (see Chapter 6), does not occur in ionic systems as macroions
the same charge repel each other and as a bearing
result the concentrations of
species are usually much higher in ionic than in free-radical systems. propagating
As ionic polymerizations with
stringent reaction conditions are more difficult
to carry out than normal free-radical
processes, the latter are invariably preferred
where both free-radical and ionic initiations
give a similar product. For example,
commercial polystyrenes are all free-radical
ization can be initiated with free radicals as products, though styrene polymer
well as with appropriate anions or
cations. However, to make research
grade polystyrenes with exceptionally narroOw
molecular-weight distributions and di-block or multi-block copolymers of styrene
and other monomers, ionic
processes are necessarily employed.
In this chapter, we will review
pure ionic polymerizations-first, anionic poly-
merizations with some of their
specific applications and then the polymerization
processes which proceed by a cationic mechanism. Coordination
that are complex polymerizations
polymerizations having partial ionic character and ring opening
polymerizations, many.of which proceed by anionic and cationic mechanisms,
will be reviewed in subsquent chapters.

8.2 Ionic Polymerizability of Monomers

The processes whereby a given alkene reacts depend on the inductive and res-
onance characteristics of the substituent X in the vinyl monomer CH2 =CHX.
Electron-releasing substituents,

R RO-, R- = and

increase the electron density of the double bond and thus facilitate addition of a
cation:
H
H
AtB ACH-ct...B" (8.2)
H xO X
Thus monomers like isobutylene (VI), 3-methylbutene-1 (VI), styrene (VIL),
and vinyl ethers (LX) all undergo cationic polymerization.
CH3
CH- CH=CH CH=CHa CH=CH
CH3 CH(CH3)2 Cly OR
(VT (VID (VI) (IX)
478
Chapter8

Electron-withdrawing substituents, such as

-CN, C-OH or -OR

decrease the electron density of the double bond and thus facilitate attack of an
anionic species on the double bond to produce an anion:
H
H H
C=C AtB- BCH CA (8.3)
H X
in acry-
The electron-withdrawing substituents may also stabilize the anion, e.g.,
carbanion oc-
lonitrile polymerization, where the stabilization of the propagating
over the a-carbon and the nitrogen
curs by delocalization of the negative charge
of the nitrile group:
H

www.CH wwww.CH2 (8:4)

C=N N
anionic polymer
shown in cationic and
Problem 8.1 Contrary to the high selectivity carbon-carbon
about the polymerization of almost any
initiators can bring free radicals. Explain,
ization, radical and ketones are not activated by
double bond. However,
aldehydes
g i v i n g reasons.

the T
Answer: requirements for attacking
and do not have stringent almost all
Radical species are neutral
propagating radical occurs with
stabilization of the
resonance
bond. Moreover,
substituents, for example,

wwww.CH2
www.CHh
C=N
CEN

www.CHh
www.CHa-¢
: wwww.CH,-CH ww.CH ÇH
wwww.CH2-ÇH wwww.cHCH

double bond. Aldeby

carbon-carbon

with almost any in electroneg-

difference
thus take place because of the ionic or
Radical
initiation can
activated by free radicals
polymerized only by
are not ketones are
ketones and
des and atoms.
Aldehydes

of the C and O
ativitygeneaus_ catalytic processes.
Ionic Chain Polymerization 479

Phenyl and alkenyl (-CH=CH2) substituents, although electron-pushing in-

ductively, can resonance stabilize the anionic propagating species in the same
manner as a cyano group [Eq. (8.4)]. Monomers such as styrene and 1,3-butadiene
can therefore undergo both anionic and cationic polymerizations.
The applicability of various types of initiation mechanisms to the polymer
ization of common olefin monomers (Lenz, 1967) is summarized in Table 8.1
We see that isobutene can be polymerized only by cationic initiation, whereas
monomers, such as vinyl chloride, methyl methacrylate, or acrylonitrile with their
electronegative substituents, will not yield at all to cationic initiation. Vinyl chlo-
ride does not also respond to anionic initiation. Though halogens can withdraw
electrons inductively and push electrons by resonance, both effects are relatively
weak. Vinyl chloride thus does not undergo either anionic or cationic polymeriza-
tion.

8.3 Anionic Polymerization

8.3.1 Anionic Initiation
While initiators for anionic polymerization are all electron donors of varying base
strengths, the initiator type required for a particular polymerization depends on
the ease with which an anion can be formed from the monomer. In general, the
strength of the base required to initiate polymerization decreases with increas-
ing electronegativity of the substituent on the monomer. The electronegativity of
some selected substituents is in the following order (Lenz, 1967):

-CN-COOR -CsHs -CH=CHh » -CH3

Since acrylonitrile has a strong electronegative substituent (-CN), it can be poly-
merized by the relatively weak sodium methoxide (NaOCH3) and vinylidene
cyanide carrying two -CN groups on the same carbon atom can be polymerized
even by weaker bases like water and amines. However, for polymerization of
nonpolar monomers such as conjugated olefins very strong bases like metal alkyls
should be used as initiators.
The principal anionic initiation processes are (a) nucleophilic attack on the
monomer which produces one-ended (monofunctional) anions by addition of the
initiator across the double bond of the monomer [see
Eq. (8.3)] and (b) electron
transfer by alkali metals that leads to wo-ended
(bifunctional) anions (see later).
8.3.1.1 Nucleophilic Attack
Nucleophilic attack on a olefinic monomer is
essentially addition of a negatively
charged entity to the monomer
[Eq. (8.3)]. Examples of some reactive bases
which can initiate in this manner are
n-C4H9Li,
CgHsCH2Na, CH3ONa, and EtMgBr. AlkyllithiumC6H5CH2Li, are NaNH2, KNH2,
compounds generally low
melting and soluble in hydrocarbon solvents. A common
example is n-butyl
 Chapter 8
480

Table 8.1 Polymerizability of Olefin Monomers by Different Processes

Cationic Anionic Coordi-
Olefin Monomer structure Free
nation
monomer
radical

Ethylene CH2=CH
Propylene CH2=CHCH3
Butene-1 CH2=CHC2Hs
Isobutene CH2=C(CH3)2
Butadiene-1,3 CH2 =CH-CH=CH2
*
Styrene CH2=CHPh
Vinyl chloride CH2=CHICl
Methacrylic
esters CH2=C(CH,)COOCHs
Vinyl ethers CH2=CHOR
Acrylonitrile CH2=CH-CN the
to high molecular weight polymer by
Symbol +signifies that the monomer can be polymerized
initiation process indicated. Source: Lenz (1967).

Initiation involves
is available as a solution in n-hexane.
lithium, which usually
addition of the metal alkyl to the olefinic monomer:
(8.5)
CHLi + CH=CHY CaHy-CH,-¢: Li
H
This type of initiation is known as monofunctional
initiation as it produces one

the addition of monomer to the

active (ionic) site. Propagation takes place by
ionic site
CH-CH-C:Li + nCH=CHY (8.6)
CgiCHCHYCH-¢T Li
H
because of their solubility in hydrocar
Alkyllithium initiators find extensive use
heavier alkali metals, such as Na and K, are
bon solvents. Alkyls and aryls of the ionic character of the Na--C
poorly soluble in hydrocarbons because of the greater
and K-C bonds.
Potassium amide initiator is used in liquid ammonia, which has high
dielectric
constant ( 22). This is one of the ionic systems in which the
active centers behave
amide
kinetically as free ions. Initiation involves the dissociation of potassium
followed by addition of amide ion to a monomer unit (Ghosh, 1990):
KNH2 K* + NH (8.7)
H H
NH+H,c=¢ HN-CH-¢ (8.8)

Styrene and other monomers can be polymerized by KNH2 in liquid ammonia.

lonic Chain Polymerization 481

8.3.1.2 Electron Transfer

Alkali metals can donate electrons to the double bonds yielding anion radicals and
positively charged, alkali-metal counterions. This may be effected either by direct
attack of the monomer on the alkali metal, or by attack on the metal through an in-
termediate compound such as naphthalene. Both result in bifunctional initiation,
that is, formation of species with two carbanionic ends.

Alkali Metals Initiation by direct attack on the alkali metal involves transfer of
the loosely held s electron from a Group IA metal atom to the monomer. A radical
ion i.e., a species having both ionic and radical centers) is formed:
H

Li+ CH=
CHg-CFL (8.9)

The radical ion may dimerize to give a dianion

H H H
2 CH-C Li Li :¢-CH-CH,-¢: Li 8.10)
X X X
The initiation process thus results in a bifunctional dicarbanion species capable of
propagating at both of its ends.
Free alkali metals may be employed as solutions in certain ether solvents, in
liquid ammonia, or as fine suspensions in inert solvents. The latter are prepared
by heating the metal above its melting point in the solvent, stirring vigorously to
form an emulsion, and then cooling to obtain a fine dispersion of the metal.

Alkali Metal Complexes Polycyclic aromatic compounds can react with alkali
metals in ether solution to produce radical ions (Szwarc, 1968). The reaction in-
volves the transfer of an electron from the alkali metal to the aromatic compound.
For sodium and naphthalene, for example,

Na' + Nat
(8.11)

Tetrahydrofuran (THF) is a useful solvent for these reactions. Sodium naph-

thalenide is formed quantitatively in this solvent, but dilution with hydrocarbons
results in precipitation of sodium and regeneration of
naphthalene
482 Chapter 8

The naphthalene anion radical (greenish-blue) rapidly transfers an electron to

a monomer such as styrene to form the radical anion (XI) (d = -CsHs) :

H H H H
ONNat+HC=CH2 C + - ¢--¢Na
H H
(XI) (8.12)
The styryl radical ion in (XI) is a resonance hybrid of two forms having both
anion and radical centers. It dimerizes by reacting at the radical ends to form a

red-colored dicarbanion (XII):

H H H H
H H
2- ¢-¢ Na Nat -CH-CH,¢T Na
H
(XI) (8.13)
The initiation process is thus similar to alkali metal initiation described earlier
cf. Eq. (8.10)]. The dimerization of radical anions is highly probable because
of their high concentrations, typically;10--10 M, and the large rate constants
(105-10 L/mol-s) for radical coupling (Odian, 1991). Anionic propagation takes
place by monomer addition at both carbanion ends of the styryl dianion:
H H
Nat -CH-CH-C: Na + (+m) ¢HC=CH

H
H
Na c-CH,- -CH¢-CH- CH-CHCH-¢: Na

(8.14)
Anionic propagation is generally much faster than free-radical reactions.
1Ollc i l a l l i fOIyilerIzation1

483
8.3.2 Termination Reactions
To carry out anionic
polymerizations,
gen, carbon dioxide, or any other
extraneous substances such as water,
oxy-
centers, must be absent. Since
impurities that may react with the active ionic
glass surfaces contain adsorbed water, special pre-
cautions are taken in laboratory
to remove this water. In
polymerizations, such as flaming under vacuum,
addition, the monomer itself should be very pure and free
from inhibitors.

8.3.2.1 Living Polymerization

Following the work of Michael Szwarc in mid 1950s, it became known that under
carefully controlled conditions carbanionic living polymers could be formed
electron transfer initiation. Because the using
growing chains in anionic polymerization,
carrying negative charges, cannot react with each
other, there is no compulsory
chain termination
through recombination. In polymerization systems, especialy
of nonpolar monomers such styrene and L,3-butadiene in perfectly dry inert
as
solvents such as benzene and tetrahydrofuran, initiated by
organometallic com-
pounds, termination or transfer is virtually nonexistent and active chain ends can
thus have indefinite lifetimes. Such
systems are referred to as living
Propagation continues till 100% conversion of the monomer is reached, polymers.
while the
propagating anionic centers remain intact and capable of fürther propagation if
more monomer (either same or
different) is added.
One of the first living anionic
polymerization systems studied was the poly-
merization of styrene initiated by sodium naphthalene
(p. 481). If the reaction
system is highly purified so that all impurities that are liable to react with the
carbanions excluded from the system, propagation continues until all
are
monomer has been consumed, but the color of the
styrene
polystyryl carbanions remains
unchanged indicating that the carbanions are intact. That the resulting
chains are still active can be easily demonstrated polymeer
by adding more styrene to in-
crease the molecular
weight or by adding another monomer,such as
form a block copolymer. [Note: There is no reason isoprene, to
in theory why chain
should not continue indefinitely if more and growth
more monomer is added and
terminators are absent. In practice, chain
however, small amounts of terminators are
invariably produced in the system and chain growth also slows down due
large increase in viscosity at high molecular to a
insoluble (Allcock and weight or due to chains
becoming
Lampe, 1990).]
The living chains can be
terminated when desired by
tive materials, such as
water, alcohol, or ammonia. The
adding suitably reac
ing polymer systems described above unique features of liv-
syntheses, which include making provide fascinating possibilities of polymer
of monodisperse polymers (by controlled addition
monomer), structures with specific end groups (by chain
termination with ap-
484

sequential addition of two or more

propriate reagents), and block copolymers (by
in a later section.
more fully
monomers). These are discussed

8.3.2.2 Termination by Transfer Agents

its CrS
Water is an especially chain terminating agent. For example, sodium
effective
of styrene at 25°C with
value is approximately 10 in the polymerization
can significantly
of even trace quantities of water
naphthalene. So the presence Water terminates
and polymerization rate.
reduce the polymer molecular weight
transfer:
propagating carbanions by proton
H H
www.CH + HO
www.CH-CH + HO (8.15)
X X
sufficiently nucleophilic to
reinitiate polymer-
The hydroxide ion formed is not
contrast, the Crns
ization and the active center is thus effectively destroyed. In
in small amounts does
value for ethanol being very small (~ 10-), its presence
not limit the molecular weight.
the atmosphere add to propagating carban-
Oxygen and carbon dioxide from
anions
ions to form peroxy and carboxyl
H
H
www.CH,-Ç: + O2 wwww.CH2 --0-0 (8.16)
x

www.CH-C + CO (8.17)
X

As these anions are not reactive enough

to continue propagation, the chains are

effectively terminated. By adding a proton

donor subsequently to the polymer-
COOH
ization system, the peroxy and carboxyl anions are converted to OH and
groups. A notable example of the application of the latter reaction is the prepara-
tion of carboxyl ion terminated polybutadiene by anionic polymerization of buta-
diene with bifunctional initiators, followed by termination with C0
H H
Nat T-CH=CH-CH,mwwww.cH-CH=CH- Na+CO
CO2
H H

Na 0--CH-CH=CH-CH, w.cHs-CH=CH-CH,--07 Na
(8.18)
Reaction with acid then yields
carboxyl-terminated polybutadiene (CTPB). Ter
Tonic Chain Polymerization
485

mination with ethylene oxide similarly generates

hydroxyl end groups
H

www.c7 Li+CH-CH, - vwww.CH-CH,-CH-0: Li CHOH

H
wwww.CHCH-CH-OH LiOCH3
(8.19)
Hydroxyl-terminated polybutadiene (HTPB) can be produced by such reac-
tions. Such elastomers of low molecular weight (3000-10,000) are used as binders
and liquid rubbers. Telechelic polymers (that is,
polymers with reactive end groups),
containing one or more end groups with the capacity to react with other molecules,
can be prepared in this
way.

8.3.2.3 Spontaneous Termination

As mentioned earlier, living polymers do not, in reality, have infinite life times
even in the complete absence of terminating agents as they undergo decay on ag-
ing, a process known as spontaneous terminatíon. Polystyryl carbanions, known
to be the most stable of all anionic chains as they can survive for weeks in hy-
drocarbon solvents, undergo spontaneous termination by a mechanism known as

hydride elimination, as shown by the equation (Odian, 1991) :

wwww.CHCHO CH-¢: Na - www.CH CH) CH=CHo + H: Na

XI) (XIV)
(8.20)
This may be followed by other reactions (Odian, 1991), such as abstraction of an
allylic hydrogen from (X) by a carbanion center (to yield an unreactive anion)
or hydrogen abstraction by the sodium hydride (XIV) formed in reaction (8.20).

8.3.3 Polymerization with Complete Dissociation of Initiator

In polymerizations initiated by alkali metals or insoluble organometallic com-
pounds used as fine dispersions in organic media, the initiation step occurs at a
phase interface while subsequent propagation reactions may occur in a homoge-
neous phase. The kinetics of such reactions combining heterogeneous initiation
and homogeneous propagation are often very complex and speciic to the given
systems. However, useful generalizations may be made for systems in which both
the initiation and propagation processes are
homogeneous.
Such are dis-
systems
cussed next.
There are some cases inhomogeneous anionic polymerization in which the
initiator dissociates completely with
ionic form and the process is also
quantitative transformation into the active
virually instantaneous (stoichiomeric polymer
ization). This is the case, for example, when one
uses, as initiators, alkali organic
 486
Chapter 8

compounds (e.g., phenyllithium, butyllithium, or sodium

which have unshared electron pairs (Lewis naphthalene) in solvents
bases).
tively charged complex ions with the Lewis base
The alkali forms stable
posi-
residue becomes negatively charged (Lenz, 1967), while the organic
(carbanion)
merization [cf. Eqs. (8.11) and (8.12)]:
and can initiate an ionic
poly-
CHLi+ CH,CH,CH-¢?

+ NH3
NH

Since the polymerization kinetics in the above cases are extremely

simple,
ionic polymerization kinetics can be conveniently classified according to whether
the initiators are quantitatively and instantaneously dissociated or not.

8.3.3.1 Polymerization Kinetics

For a kinetic analysis, the process of anionic polymerization is divided in the con-
ventional way into three main steps, viz., initiation, propagation, and termination.
Representing the initiator by CA (or C"A") and a terminating agent by X, the
reactions can be written (Allcock and Lampe, 1990) as:

Initiation: CA + M AM Ct (8.21)
Propagation: AM C* + M AMM-c* (8.22)
AMM C* +M AMMM" C* (8.23)
AM,-1M" ct+ M AM,M" C* (8.24)
Termination: AM,MC* (+X)> AM,M (8.25)
(Depending on the solvent used, the propagating ion may behave as a free ion
AM,M" or as an ion pair AMMC", or as both.) Living pohymerizations are
characterized by the absence of termination (as well as transfer) reactions. The
initiators in most cases are reactive enough to give instantaneous initiation, i.e.
ki >kp, which implies that no initiationtakesplace during the polymerization and
the number of chain (growth) centers to which the monomer molecules may add
reaches its maximum value before polymerizarion begins. There is, moreover, no
change in the number of chain centers during the polymerization as there is no
 Tonic Chain Polymerization 487

chain termination. the total concentration of anions (of all degrees of

Denoting
polymerization) by [M] (the positive counterion C* is not shown for simplicity)
and assuming that the initiation reaction (8.21) is both instantaneous and com-
plete, one can write: [M] = [CA] (8.26)
Hence the rate of polymerization is given by
Rp -d[M]/dt = k, [MJ[M] = k, [CA]l [M]1 (8.27)
The rate constant k, is, in fact, an apparent rate constant or overall rate constant
since there will be both undissociated (ion pair) and dissociated (free ions) species
in the polymerization system and their propagation rate constants are different
(discussed later). Integrating Eq. (8.27) one obtains the time dependence of
the
monomer concentration as

[M] =
[Mlspexp(-kp[CA]) =
([M-[CA],)exp(-kp[CAJ4) (8.28)
where the subscript ' ' indicates initial value and [Msp represents the monomer
concentration at the start of propagation [Eq. (8.22)j, that is, the original monomer
concentration less the concentration of the initiator CA which is quantitatively
reacted in the initiation step [Eq. (8.21)]. Using [M] measured at various times
after the polymerization is started and knowing [MJo and [CA]o, one may thus
determine kp. The significance of kp will be discussed in a later section.
8.3.3.3 Average Kinetic Chain Length
As there is no termination step in a true living polymerization, the growth of
chains, once initiated, can stop only when the monomer is completely consumed.
In living polymerization with fast and complete dissociation of initiators the
a

average kinetic chain length will thus be given by

,

Monomer molecules consumed [Msp M]

(8.29)
where
Number of chain centers [CA]
[Msp [M - [CAl (8.30)
 lonic Chain Polymerization
489

Substituting [M] from Eq. (8.28), v is given as a function of tirme (t) by

y = Msp (1 e
CAT-eko[CA}ot
(8.31)
The maximum value of v is obtained the
at completion of reaction or in the limit
of too as
Voo [Msp
[CA] (8.32)

8.3.3.4 Average Degree of Polymerization

The average degree of polymerization represents the average number of monomer
molecules polymerized per polymer molecule formed. In the case of monofunc-
tional initiation [cf. Eq. (8.5)], the number of polymer molecules formed is
equal
to the number of chain centers (or initiators) and the number
average degree of
polymerization then is [cf. Eq. (8.29)]

DP = [M),-[M] (Msp +[CAJ) -

[M]
[CA]
V+1 (8.33)
[CA]
In the case of bifunctional initiation that produces double-ended active species
cf. Eq. (8.10)J, the number of polymer molecules formed is 1/2 of the number of
chain centers orinitiators. The average degree of polymerization is then given by
DP M - [M] ((M]sp + [CA]o) - [M] 20v + 1)
(8.34)
ICA) ICAJ
 8.5 Cationic Polymerization
As we saw in Section 8.2, the active center in cationic polymerization is a cation
and the monomer must therefore behave as a nucleophile (electron donor) in
the propagation reaction. Suitability of monomers for cationic
polymerization
was also discussed in that section and compared in Table 8.1. In short, olefinic
monomers with an electron-releasing or electron-donating substituent on the a-
carbon can undergo cationic polymerization, while the possibility of resonance
stabilization of the carbocationic species increases the reactivity of the monomer
(see Problem 8.15).

Problem 8.15 Compare the cationic polymerizability of (a) ethylene, propylene, and
isobutylene; (b) styrene, a-methylstyrene, p-methoxystyTene, and p-chlorostyrene.
Answer
(a) The electron-releasing alkyl groups cause isobutylene to polymerize readily at low tem-
peratures (yielding high polymer),whereas propylene reacts only with difficulty, yielding
low-molecular weight polymers, and ethylene is nearly unreactive. Also from a considera
tion of carbocation stability (i.e., tertiary most stable, followed
by secondary and primary)
the polymerizability is in the order

HC=CH > " CH> H=CH

HC H

(b) Conjugation when present helps to disperse the positive charge of the carbocation cen-
ter thus increasing the reactivity of the monomer. The effect becomes
stronger when con-
jugation and electron-donating groups cooperate. On the other hand, substitution of an
electron-withdrawing halogen for an ortho or a para hydrogen decreases the monomer
reactivity. Thus the reactivity sequence of the styrene derivatives is as follows:

CH H,C HCH H CH

>
OCH CI
By similar reasoning, electron-releasing substituents, such as RO-, RS-, and
or para
aryl at ortho
position, increase the monomer reactivity for cationic polynerization.
 Tonic Chain Polymerization 513

8.5.1 Cationic Initiation

are known to initiate cationic polymerization of
Two main classes of compounds
are the strong protonic acids and Lewis
olefins and olefinic derivatives. These
acids.

8.5.1.1 Protonic Acids

The cationic initiation reaction involving a monomer and a protonic acid HA can

be written as

HA +
CH CH-C+ A (8.100)
R
not be a strong nucle-
For polymerization to occur, the anion A", however, should
to form the nonpropagating
ophile, as otherwise it will react with the carbocation
covalent compound
CH--A
ions fail to
This explains why hydrogen halides with highly nucleophilic halide
initiate cationic polymerization.

8.5.1.2 Lewis Acids

Lewis acids are halides and halides of Group II metals and of transition
alkyl
metals which have incomplete d electron
shells. These constitute the most use-
halides (e.g., BF3, AICl3, SnCl4, PCls.
ful group of initiators and include metal
derivatives (e.g., RAICl2, R2AlCI, R3Al).
SbCls, TiCl4) and organometallic
seldom effective alone as initiators
Most or perhaps all of the Lewis acids are
or catalysts; they are used
in conjunction with a second compound, called a 'co
which often is water or some other proton donor (protogen) such
catalyst', very
as hydrogen halide, alcohol,
and carboxylic acid, or a carbocation donor (cationo-
chloride and triphenylmethyl chloride. On reaction with the
gen) such as -butyl
that initiates polymerization.
Lewis acid, they form a catalyst-cocatalyst complex
boron trifluoride if both are dry,
For example, isobutylene is not polymerized by
a small amount of water. The
but immediate polymerization takes place on adding
initiation process is therefore represented by
BF3 +H20 H*(BFOH)" (8.101)
(CH3)hC CH2 (CH3)3C* (BF%OH) (8.102)
H (BF3OH)+ =

de-
aluminum chloride with r-butyl chloride cocatalyst is similarly
Initiation by
scribed by
(8.103)
AICl + (CH3)3CCI (CH3)3C* (AICl,)
OCH CH2 (CH3)CCH2CHo(AIClL) (8.104)
(CH3)3C*(AICL) + =
 Chapter 8
514

The initiation steps described above can be generalized as

L+IB B*(LI) (8.105)
B (LI)+ M BM* (LI) (8.106)
where L is a Lewis acid catalyst, IB is an ionizable compound acting as the co-
catalyst, and M is a monomer. Initiation by the catalyst-cocatalyst system has the
advantage over initiation by a Brönsted acid (H*A") that the anion (LI) is far
less nucleophilic (Odian, 1991) than A" [cf. Eq. (8.100)].

8.5.2 Propagation of Cationic Chain

The propagation of a cationic chain occurs by successive addition of monomer
molecules to the initiator ion pair produced in the initiation step [Eq. (8.106)]. In
general terms, the propagation can be represented by

HM,M* (LD + M HMa+1M* (L)- (8.107)

which shows that the reaction involves insertion of monomer between the carbo-
cation and its negative counterion. Thus in the polymerization of isobutylene, the
cationic chain propagation step is (Odian, 1991):
H4CHC(CHs)2i-CH2(CHs» (BF;OH) + (CH;)2C=CH2
H4CHC(CHs)2ia+t-CH2(CH;)2 (BF3OH)" (8.108)
In some cases, the propagation reaction is accompanied by intramolecular re-
arrangements due to hydride ion (H:") or methide ion (CH3:") shifts. Such poly-
merizations are referred to as isomerization polymerizations. Consider, for ex-
ample, the polymerization of 3-methyl-1,2-butene in which the carbocation (XV),
formed initially, isomerizes by a 1,2-hydride shift. The resulting ion
(XVI), being
a tertiary carbocation, is more stable than
(XV) which is a secondary carbocation.
H
wwww.CH -¢* wwww.CH-CH-C(CH3)2
CH(CH3)2
XV) CXVT)
Propagation thus mostly by (XVI), apart from some normal
occurs
by (XV) at higher temperatures. The polymer will therefore containpropagation
mostly the
rearranged repeating unit (XVI) and a smaller number of the first formed repeat
unit (XVI). This expectation is
supported by the observation that the product
contains about 70 and 100% of (XVII) at
and
polymerization
temperatures of -130
-100C, respectively (Kennedy et al., 1964; Odian, 1991).
 515

ww.CH-CH2-C(CH3), ww ww.CH-CHww.
H CCH)2
CXVI)
(XVI)
The cationic
polymerization of propylene, 1-butene, and higher 1-alkenes
yields only very low molecular weight polymers (DP
complicated structures that arise due to various combinations10 - 20) with highly
of
1,2-methide shifts, proton transfer, and elimination, besides chain1,2-hydride and
transfer during
polymerization. In the
polymerization of ethylene, initiation involving protona-
tion and ethylation is
quickly followed by energetically favorable isomerization:
H CH2 =CH2 CH CH, CH=CH
H:
CHCH-CH2-CH2 * CH,CH2-CH-CH3 etc. (8.109)
These transformations are facilitated by the fayorable
tween enthalpy differences be-
primary to secondary (-92 kJ/mol) and secondary to tertiary ( -138
kJ/mol) carbocations

Problem 8.16 Write equations to show the different structural units that
result from
intramolecular hydride and methide shifts involving only the end unit in themay
cationic poly-
merization of 4-methyl-1-pentene. Which of the
most abundant ?
resulting repeating units would be the
Answer:
Five different end units (XLX-XXIII) may arise from
1,2-hydride and methide shifts. The
first-formed carbocation (XIX) undergoes hydride shifts to form carbocations
and (XXII); (XXI) rearranges to (XXII) by a methide shift (XX), (XXI).
(Kennedy and Johnston, 1975;
Odian, 1991)
H H

CH=ÇH mCH-C mc
CHCH(CHh CH,CH(CH) CHCH,CH(CH,)%
CXDX) (XX)
Hshift
CH H
CH H
+ H:shift mCH,CH,-c* shift
mCH,CH,CH, C
mCH,CHCH-C
CH CH(CH, CH
(XXI) XXD (XXIn
As the tertiary carbocation (XXII) i_ the most stable, the repeating units derived trom it
will be expected to be most abundant (found 42-51%
(Odian, 1991).
 516 Chapter8

8.5.3 Chain Transfer and Termination

While termination of chain growth in cationic polymerization may take place in
various ways, many of the termination reactions are, in fact, chain transfer reac-
tions in which the termination of growth of a propagating chain is accompanied
by the generation of a new propagating species.

8.5.3.1 Chain Transfer to Monomer

In general terms, chain transfer to monomer can be written

BM,M* LI) + M Ker.M Ma+l + BM* (LI) (8.110)

Chain transfer to vinyl monomer involves transfer of a B-proton from the carbo-
cation to a monomer molecule. Considering, for example, the polymerization of
isobutylene, the chain transfer to monomer can be represented by the equation
HCH2C(CH3)2i-CH2 C(CH3)2(BF,OH)" + CH2 =C(CH3)2
(CHs)C* (BF,OH)" + H4CH;C(CH3)hir-CH2C(CH;)=CH2
H4CH2C(CH3)2-CH=C(CHs)2 (8.111)
which shows the formation of two different unsaturated groups, since there are
two different types of F-protons.
As a new propagating species is generated each time a growing chain is ter
minated by transfer to monomer, many polymer molecules can result for each
molecule of catalyst-cocatalyst complex initially formed.
The ratio k,M/kp defines the monomer chain transfer constant CM and, as in
the case of free-radical polymerization (Section 6.8.1), its value determines the
polymer molecular weight, in the absence of other chain termination processes.
Another type of chain transfer to monomer involves hydride ion transfer from
monomer to the propagating center (Kennedy and Squires, 1965, 1967; Odian,
1991):
H4CHC(CHs)hi-CH; CCHs»(BF;OH) + CH=C(CHsh
CH-C(CH,)H; (BF,OH) + H4CH2C(CH)hi-CH%CH(CH3)2 (8.112)
Note that this transfer reaction results in saturated end groups, unlike proton trans-
fer reaction [Eq. (8.111)) which gives riseto an unsaturated end group. Theally
carbocation formed by the hydride transfer [Eq. (8.112)) is less stable than the
tertiary carbocation formed by proton transfer [Eq. (8.111)). For isobutylene,
hydride transfer is thus less likely than proton transfer
8.5.3.2 Spontaneous Termination
Spontaneous termination, also refeed to as Chain ransfer to counterion, is the
unimolecular rearrangement of the ion-pair which results in termination of the
growing chain and simultaneous regeneration of the catalyst-cocatalystcomplex.
 Tonic Chain Polymerization
517

This be
represented in general terms bby
can

BM,M* (LI) Kts Mn+1 +B (LI)

The kinetic chain is thus not terminated and the (8.113)
a terminal unsaturation. For
polymer molecule formed bears
example, for the system isobutylene/BF3/H20, the
reaction is represented (Odian, 1991;
Billmeyer, Jr., 1994) by:
H-CH2C(CH3)2J-CH2 C(CH3)2 (BF3OH) -

H (BF3OH) +
H--CH2C(CH3)2H-CH2C(CH3)=CH2 (8.114)

8.5.3.3 Combination with Counterion

This process, unlike the above mentioned processes, terminates the kinetic chain.
in general terms, the reaction can be represented by

BM,M(LI) S BM,MLI (8.115)

This type of termination occurs, for example, in the trifluoroacetic acid initiated
polymerization of styrene (Throssell et al., 1956; Odian, 1991; Billmeyer, Jr.,
1994): H C H
ww.CH,-¢t :OCF www.CH,¢-0-CCF (8.116)

O O
The propagating ion may also combine with an anionic fragment from the, coun-
terion (Kennedy and Feinberg, 1978; Odian, 1991) as in BX3.OH2 (X = halo

gen) initiated polymerization or terminate by alkylation or hydridation (Kennedy,

halide initi-
1976; Reibel et al., 1979; Odian, 1991) when aluminium alkyl-alkyl
ating sytems are used.
 8.5.3.4 Transfer to SolventslReagents
The termination of growth of individual chains can occur by chain transfer to
solvent or impurity present in the
system, or to a transfer agent (denoted here by
TA or S) deliberately added to thè
system. In general terms, the reaction can be
represented by
BM,M*(LI) + S(TA) BM,MA +T (LI) (8.117)
involving the transfer of a negative fragment A". The term
krS, as in Chapter
6, is used to denote the rate constant for chain transfer to solvent or
any other
transfer agent. Common examples of such transfer agents are
water, alcohols,
and acids. Termination by these
compounds involves the transfer of HO, RO, or
RCOO anion to the chain carbocation (Mathieson, 1963;
Odian, 1991), e.g.,
www.CH2C(CH3)2 (BF3OH) + HO
www.CH2C(CH3)2OH + H* (BF3OH) (8.118)
Water, alcohols, acids, and amines are thus used to quench a cationic
ization. These are added in excess to terminate the
polymer-
polymerization when desired,
usually after complete or maximum conversion of the monomer has been attained.
8.5.3.5 Chain Transfer to Polymer
In polymerizations of 1-alkenes such as propylene, intermolecular hydride trans-
fer to polymer can occur giving rise to short chain branches. Such transfer is
explained by the fact that propagating carbocations being reactive secondary car-
bocations can abstract tertiary hydrogens from the polymer (Plesch, 1953; Odian,
1991). For example, reaction (8.119) produces a relatively stable tertiary carbo-
cation from a more reactive propagating secondary carbocation.
H H
ww.CH-CT (BFOH) + ww.CHC-CHw
CH CH CH,www
www.CH-CH-CH+ ww.CH (BF,OH) (8.119)
CH3
The reaction contributes to the formation of low-molecular weight products from
1-alkenes.