6.0 Ionic Polymerization 2015

Anionic, cationic and
coordination
References
1. Joel R Fried (1995), Polymer Science and Technology,
Prentice Hall, NY.
2. George Odian (2003), Principles of Polymerization, 4th
Edition, Wiley Interscience, NJ.
3. D. Braun, H. Cherdron, M. Rehahn, H. Ritter, B.
Voit (2005), Polymer Synthesis: Theory and Practice
Fundamentals, Methods, Experiments, 4th Edition,
Springer-Verlag Berlin Heidelberg, Berlin.
Ionic polymerization
SLIDE 2
1.0 Introduction
Follow the same basic steps as free-radical
polymerization (i.e. initiation, propagation and
termination)
However, the ionic site is either a carbanion (C ) for
anionic polymerization or a carbonium (C ) for cationic
polymerization of C=C compounds.
SLIDE 3
There is no chain termination by combination, since the

growing chains (macroions) repel each other
electrostatically because of their same charges.
Chain termination occurs only by reaction of the
growing chain ends with substances such as water,
alcohols, acids, and amines.
In contrast to radical polymerizations, ionic
polymerizations can proceed at high rates @ at low
temperatures, since the initiation and propagation
reactions have only small activation energies.
For example, isobutylene is polymerized commercially
with boron trifluoride (BF3) in liquid propane at -100 C.
SLIDE 4
The ionically polymerizable monomers includes

compounds containing a C=C, C=O or a C=N group
and a series of heterocyclic compounds.
The tendency of these compounds to undergo cationic
or anionic or both mechanisms depend to the type of
substituent at the double bond.
The unsaturated compounds with electronwithdrawing substituents (carboxyalkyl, nitro, nitrile,
vinyl) will initiate anionic polymerization (by OH ,
NH2 or carbanions).
The addition of the anion takes place at the
unsubstituted carbon atom, which carries a partial
positive charge.
SLIDE 5
For cationic polymerization, electron repelling groups

(alkyl, phenyl, alkoxy) cause polarization and make the
unsubstituted carbon atom of the double bond carries a
partial negative charge.
Protons or other suitable cations with positive charges
can attach themselves to the unsubstituted carbon,
which indirectly add monomer by the propagating
reaction.
An ionic polymerization which can propagate
streospecifically will lead to tactic polymers.
SLIDE 6
1.1 Solvents
Solvents are important in ionic polymerization. They are
used to disperse a molten alkali metal suspension
initiators.
High polar hydroxylic solvents such as water and alcohol
cannot be used to solvate* the ions as they can react with
initiators and destroy them.
Other polar solvents such as ketones will prevent
initiation of polymerization by forming highly stable
complexes with the initiators.
*Solvation is a process of attraction and association of
molecules of a solvent with molecules or ions of a
solute. As ions dissolve in a solvent, they spread out
and become surrounded by solvent molecules.
Solvents of low or moderate polarity such as

tetrahydrofuran, ethylene dichloride, pentane and
nitrobenzene are usually used in ionic polymerizations.
In solvents, there are 4 types of possible propagating
species. For any propagating species such as
BA ,the
range of behaviors can exist as a completely covalent
species (I) to a completely free (and highly solvated)
ion (IV).
The intermediate species include the tight or contact
ion pair (II) (or intimate ion pair) and the solventseparated or loose ion pair (III).
B+ A-
BA
I
II
B+//AIII
B+ + AIV
SLIDE 8
B+ A-
BA
I
II
B+//AIII
B+ + AIV
The intimate ion pair has a counter- or gegenion of

opposite charge close to the propagating center
(unseparated by solvent).
The solvent-separated ion pair involves ions that are
partially separated by solvent molecules.
The propagating cationic chain end has a negative
counterion while for an anionic polymerization has a
positive counterion (i.e. B carries the negative charge
and A the positive charge).
SLIDE 9
Most ionic polymerizations involve types II, III and

IV propagating species, depends especially the
solvent employed.
Increased solvent polarity favours the loose ion pair
(III) while the low polarity predominates tight ion
pair (II).
The covalent species (I) is usually unreactive (or
much lower reactivity) and negligible.
Free-ion species (IV) exist in smaller concentrations
but more reactive than ion pairs (II and III)
especially in anionic polymerization due to smaller
size counterions .
Increase solvent polarity will shift ion pairs to free
ions.
10
1.2 Anionic polymerization

Anionic polymerization is a chain reaction
polymerization in which the active species is an anion
(i.e. an atom or group with a negative charge and an
unshared pair of electrons).
These anions are associated with a counterion which
typically is an alkali metal cation.
The initiator in anionic polymerization may be any
strong nucleophile, including Grignard reagents* and
other organometallic compounds like alkyl lithium,
diethylzinc and organomagnesium.
*
The chemical formula of a Grignard reagent can be given as RMgX,

where R is an alkyl, aryl or other organic group and X is halogen, especially
Cl, Br or I.
SLIDE 11
Polymerizations with organometallic compounds as

initiators are generally carried out in solution.
Initiation starts with heterolytic cleavage of the lithiumcarbon covalent bond to give ions.
n-C4H9Li
n-C4H9 Li
Initiation proceeds by addition of the n-butyl lithium

initiator across the double bond of monomer.
R1
H2C
CH
R1
R M
CH2
R1 represents an electron withdrawing group such as

phenyl or cyano.
12
The extensive use of alkyl lithium initiators is due to

their solubility in hydrocarbon solvents.
Alkyls or aryls of the heavier alkali metals are poorly
soluble in hydrocarbons due to their more ionic nature.
Propagation involves the successive insertion of
monomer molecules into the terminal ionic bond.
The chain growth continues until all the monomer has
been consumed or the reaction is terminated.
R1
R1
R
CH2
CH2
R
H
R1
CH2
R1
H2 C
CH
13
Chain transfer or chain branching does not occur to

certain anionic systems if the reaction is carried out at
lower temperatures.
Termination occurs either accidently or deliberately
when active chain end reacts with a molecule of water,
alcohols or protonic reagents.
In practical, it is impossible to remove all traces of
water molecules.
R1
H2C
R1
R
C
H
H 2O
CO
fo
llo
HC wed
by
l
MOH
R1
H2C
COOH
MCl
14
Summary
carbanion
propagating species
SLIDE 15
Example 1:
Bu
Li
H2C
CH
HBu
3C
CH2
CH
Li
During the initiation process, the addition of the butyl

anion to styrene produces carbanion at the head end, in
association with the positively-charged lithium
counterion.
If the starting reagents are pure and all oxygen and traces
of water are purged out of reactor, propagation can
proceed indefinitely or until all monomers are consumed
(i.e. living polymerization)
SLIDE 16
1.3 Living anionic polymerization

A living polymerization is a chain polymerization that
proceeds in the absence of the kinetic steps of
termination and chain transfer.
It capable of continuing chain growth if more or same
monomer or second monomer is added.
Chain growth will slow down eventually because the
increase viscosity of the system or because the polymer
chains became insoluble.
Initiators that able to produce living polymerization are
those which form radical anions during the initiation
process e.g. sodium napthalenide.
17
Initiation occurs when an electron is transferred from

Na to monomer to generate a radial anion.
R
H2C
Na
H2C
Na
Na
Dimerization of the radical anion takes place to form a

dianion.
R
Na
C
H
R
CH2
H2C
Na
Na
C
H
R
CH2
CH2
Na
18
Propagation can occur at both ends of dimer by the

insertion of the monomer molecules into the ionic
R
R
bonds.
Na
CH2
CH2
Na
The napthalene radical anion either transfers an

electron to the monomer to form a monomer radicals
anion or the radical anion itself initiates monomer
polymerization directly.
The initiating species e.g. Na napthalene, is
incorporated as end group of the terminated-polymer
chain.
Na
Napthalene
radical anion
19
In the absence of a termination mechanism, the rate of

initiation that competitive with or faster than the rate of
propagation, thus each monomer has an equal probability
of attaching to an anion site.
This condition ensures that all of the chains grow in the
same period of time, leads to a very narrow MWD
(monodisperse) with polydispersities ~ 1.06.
By comparison, polydispersities for typical free radical
polymerization are 2-20.
Using these concepts, it is possible to synthesize
macromolecular compounds with control of a wide range
of compositional and structural parameters such as MW,
MWD, copolymer composition and microstructure,
stereochemistry, branching and chain-end functionality.
SLIDE 20
Many anionic chain ends remain alive in the absence of

monomer especially at low temperature.
Chain growth (AAA) can be restarted by the addition
of second monomer (BBB) to form copolymer.
CCCCBBBBBBAAAAACH
2---CH2AAAAABBBBBCCCC
The monomers should have similar electron affinities

for reinitiation is to take place.
If monomer B (e.g. MMA) has higher electron affinity
(powerful electron withdrawing group) than A (e.g.
styrene), the addition of A monomer will not initiate
the propagation of an A-block.
If a polar monomer C (e.g. AN) is added, then the
propagation of C will take place.
SLIDE 21
1.4 Cationic polymerization

Cationic polymerizations are usually conducted in
solution and at low temperature, typically -800 C to 1000 C which provides satisfactory polymerization rates.
The choice of solvent is important because the solvents
intimate association between cation and counterion (i.e.
a tight association) will prevent monomer insertion
during propagation.
The rate of polymerization and the molecular weight
increase with increasing polarity and relative
permittivity (dielectric constant)* of the solvent.
* A dielectric is a non-conducting substance, i.e. an insulator.
Dielectric constant, k, is the ratio of the field without the dielectric (Eo) to the net field (E) with
the dielectric: k = Eo/E
Slide 22
Termination reactions can be neglected in very pure

cationic systems but slight traces of impurities can exert
significant effects because of the great reactivity of the
propagating species.
Impurities can act as co-catalysts by accelerating the
polymerization or as inhibitors (e.g. tertiary amines).
The very small amount of impurities (10 mol% or less)
can enhance the chain transfer or chain termination but
reduce the degree of polymerization.
SLIDE 23
Initiation
Various initiators with electron-releasing substituent can be
used to polymerize the monomers .
I) Protonic Acids
Protonic (Brnsted) acids initiate cationic polymerization
by protonation of the olefin.
Proton acids with unreactive
counterions
Protonic acids
Monomer
Carbonium
ion
Note:
Brnsted acids involve the transfer of an H+ ion, or proton. HCl and H2SO4 are acids that
have hydrogen that can be released as protons, they are called protonic acids. The protonic
acids help increase the concentration of the hydronium ion of water.
SLIDE 24
Strong protonic acids in nonaqueous media liberate

protons by the conventional ionization processess.
H 2SO 4
HSO -4
HClO 4
ClO-4
HCl
Cl
The use of a strong acid can produce the protonated

species, but the counterion /anion (-ve ion) of the acid
should not be highly nucleophilic; to avoid the
termination of the protonated olefin by combination
(i.e. by covalent bond formation).
Termination of
the protonated
olefin
SLIDE 25
Other strong acids with less nucleophilic anions (e.g.

sulfuric and phosphoric acids ) can be used as
initiator but will produce the low MW polymers
that less than a few thousand.
Hydrogen halides are ineffective as initiators of
cationic polymerization because of the highly
nucleophilic character of halide ions.
The requirement for the less nucleophilic anion
limits the utility of most strong acids as cationic
initiators.
26
II) Lewis Acid

Various Lewis acids are used to initiate cationic
polymerization @ low temperatures, with high
molecular-weight polymers in high yield.
These include metal halides (e.g. AlCl3, BF3, SnCl4, SbCl5,
ZnCl2, TiCl4) and their organometallic derivatives.
The initiation mechanism can be hastened in the
presence of co-initiators/co-catalyst that form ionic
complexes with Lewis acids.
Co-catalyst can be i) proton-donating compounds e.g.
Brnsted acids, water, alcohols or ii) carbanion-donor
compounds such as alkyl halides (e.g. t-butyl chloride),
ester, ether or anhydride
27
The ionic complexes then dissociate to give cations

that capable of initiating polymerization.
Lewis acid
co-catalyst
Ionic complexes
dissociate
An optimum ratio of catalyst:co-catalyst is 1:1.

Larger amounts of co-catalyst decrease the reaction
rate by destruction of the catalyst and lowering the cocatalyst concentration below the optimum amount
lowers the polymerization rate.
SLIDE 28
In the case of water or alcohol as co-catalyst, the real

initiator is a proton. Thus, dry isobutylene is
unaffected by dry BF3 but polymerization occurs
immediately when trace amounts of water are added.
H3C
BF3
H2O
H2C
CH3
H3C
C
CH3
C [BF OH]
3
CH3
Isobutylene
carbonium
Counterion
In this case, co-catalyst (i.e. water) is required to

provide the actual proton source.
Proton addition yields an isobutylene carbonium ion
that forms an association with a BF3OH counterion.
Slide 29
The carbonium ion then add to the double bond of

another isobutylene molecule during propagation
CH3
CH3
H3C
C [BF3OH]
CH3
H2C
C
H3C
H3C
H3C
C
H3C
CH3
CH2
C [BF OH]
3
CH3
Cationic initiator is restored at the end of the

polymerization and does not take part to the
termination stage.
Slide 30
Disassociation of Lewis acid with co-catalyst
Alkyl halide
carbonium
SLIDE 31
The initiation of a monomer molecule involves the

addition of proton of the catalyst across the double
bond of carbon atom that bears the biggest electron
density to form the stable carbonium ion.
R
H X
H2C
C
H
R
H2CH
The propagation mechanism takes place by successive

insertion of monomer molecules into the cation-anion
bond.
Electron donating groups (R) are needed to stabilize
the propagating species by resonance means.
32
SLIDE 33
Propagation is usually very fast. Therefore, cationic vinyl

polymerizations must often be run at low temperatures.
Termination of the polymer chain can occur by chain
transfer mechanism or by loss of a proton to the Xcounterion or by the reaction of a growing chain end with
traces of water or other protonic reagents.
R
R1
R
H2O
COH
HX
Termination by combination of two cationic polymer chains

cannot occur.
SLIDE 34
Chain transfer involves the donation of a proton from a

terminal side group to a monomer molecule.
R
CH3
H3C
C
R
H2 C
CH2
H3 C
C
R
R1
H3C
The newly initiated monomer molecule can generate a

new chain.
If more chains are initiated in this way, the average
chain length will reduce.
To get high molecular weight polymer, it is needed to
maintain low reaction temperatures.
35
Apart from chain transfer of carbonium to monomer,

other numerous side reactions can lead to chain
transfer.
1. Intramolecular electrophilic aromatic substitution
(or backbiting) occurs in the polymerization of
styrene as well as other aromatic monomers with
the formation of terminal indanyl structures and
regeneration of the initiatorcocatalyst complex.
2. The propagating carboniums can abstract tertiary
hydrogens from the polymer (spontaneous ejection
of HX)
These side reactions can be minimized but not
eliminated by running the reaction at low temperature.
36
SLIDE 37
1.5 Living cationic polymerization

It is known that cationic polymerization process could
not produce living polymers due to unstable chain
transfer process to the monomer.
However, it was found that with certain initiator
derived from tertiary esters such as t-butyl acetate-BF3
complex, are capable of initiating a living
polyisobutylene polymer.
It is suggested that an initiating complex is formed
and induced the insertion of an isobutylene molecule.
None of the cationic living polymerization systems are
as long-lived as the anionic systems.
38
The various cationic living systems show the

characteristics of living systems as long as monomer
is present, but decay of propagating species begins
in the absence of monomer.
The half-lives for propagating species in the absence
of monomer vary from less than an hour to many
hours at the higher temperatures or a day or more
for lower temperatures depending on the particular
system
The lifetimes for the isobutylene systems appear to
be lower than those for other monomers, probably
only minutes.
39
Examples of Commercial Cationic

Polymers
SLIDE 40
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Anionic, cationic and

There is no chain termination by combination, since the

The ionically polymerizable monomers includes

For cationic polymerization, electron repelling groups

Solvents of low or moderate polarity such as

The intimate ion pair has a counter- or gegenion of

Most ionic polymerizations involve types II, III and

1.2 Anionic polymerization

The chemical formula of a Grignard reagent can be given as RMgX,

Polymerizations with organometallic compounds as

Initiation proceeds by addition of the n-butyl lithium

R1 represents an electron withdrawing group such as

The extensive use of alkyl lithium initiators is due to

Chain transfer or chain branching does not occur to

During the initiation process, the addition of the butyl

1.3 Living anionic polymerization

Initiation occurs when an electron is transferred from

Dimerization of the radical anion takes place to form a

Propagation can occur at both ends of dimer by the

The napthalene radical anion either transfers an

In the absence of a termination mechanism, the rate of

Many anionic chain ends remain alive in the absence of

The monomers should have similar electron affinities

1.4 Cationic polymerization

Termination reactions can be neglected in very pure

Strong protonic acids in nonaqueous media liberate

The use of a strong acid can produce the protonated

Other strong acids with less nucleophilic anions (e.g.

II) Lewis Acid

The ionic complexes then dissociate to give cations

An optimum ratio of catalyst:co-catalyst is 1:1.

In the case of water or alcohol as co-catalyst, the real

In this case, co-catalyst (i.e. water) is required to

The carbonium ion then add to the double bond of

Cationic initiator is restored at the end of the

Disassociation of Lewis acid with co-catalyst

The initiation of a monomer molecule involves the

The propagation mechanism takes place by successive

Propagation is usually very fast. Therefore, cationic vinyl

Termination by combination of two cationic polymer chains

Chain transfer involves the donation of a proton from a

The newly initiated monomer molecule can generate a

Apart from chain transfer of carbonium to monomer,

1.5 Living cationic polymerization

The various cationic living systems show the

Examples of Commercial Cationic

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