Ionic Polymerization

Ionic polymerization takes place at lower temperatures and

can offer control of stereoregularity.
Free radicals are less selective and can polymerize most types
of monomers. Ionic needs electron donating or withdrawing
groups.
Initiation
I R*(cation/anion)
M + R+ MR+
M + R- MR-

M + e-
.M-

M – e-
.M+

Counterion(gegenions) present in the reaction medium to preserve

electrical neutrality
Much more complex than radical
polymerization.

Reaction rates much rapid,

difficult to reproduce,

small quantities of impurities can serve as

cocatalyst and influence the polymerization
rate.
Cationic polymerization
Propagating species is carbocation

Initiation: by protic acids

+
HA + CH2 CHY CH3CHY
A-
Lewis Acids: used for the initiation of cationic polymerization.
These include metal halides[MXn] (AlCl3, BF3, SnCl4, SnCl5, TiCl4,
PCl5) organometallic derivatives(RAlCl2, R2AlCl, R3Al)
Oxyhalides(POCl3, CrO2Cl).
Requires/proceeds faster in the presence of proton donor[SH](water,
alcohol, hydrogenhalide, carboxylic acid), carbocation donor(t-butyl
chloride, triphenylmethyl chloride). They are referred as initiators
and the lewis acid as co-initiator.

H2C=CH2 + H+[SMXn]- [H2C=CH2][SMXn]-

+
[H2C=CH2][SMXn]-
 BF3 + H2O  BF3.OH2

BF3.OH2 + (CH3)2C=CH2 (CH3)3C+(BF3OH)-

Propagation
+ (CH3)2C=CH2 (CH3)3CCH2C+(CH3)2(BF3OH)-
(CH3)3C+(BF3OH)-

Propagation is usually very fast. Therefore, cationic vinyl

polymerizations must often be run at low temperatures. Unfortunately,
cooling large reactors is difficult and expensive.
Also, the reaction can be inhibited by water if present in more than
trace amounts, so careful drying of ingredients is necessary (another
expense).

Propagation strongly influenced by the nature of counterion and the

solvent, stability of cation/anion
 Termination
Termination never by coupling
Chain transfer
Spontaneous termination: termination by rearrangement of the
propagating ion pair. CH3
(CH3)3CCH2C+(CH3)2(BF3OH)- (CH3)3CCH2C=CH2 + BF3.OH2

Combination with counterion: combination of the propagating center

with the counterion
OH
(CH3)3CCH2C(CH3)2
+
(CH3)3CCH2C (CH3)2(BF3OH) - + BF3

Back biting

Free radical: Termination by oxygen

Ionic: Not terminated by oxygen but by other impurities e.g. water
 DP = RP
Rt+ Rts + Rtr.M + Rtr.S

1/DP = kt/ kp[M] + kts/ kp[M] + CM + Cs [S] / [M]

Effect of reaction medium

Increased solvent polarity favors the initiation step where a charged
species is being generated.

~ A ~ + A- ~ + A- ~ +
+ A-
Solvented ions
Intimate Solvent-
Covalent ion pair separated
ion pair
More intimate the association between the ion pairs, the lower the
propagation rate. Hence increase in solvent polarity facilitates propagationbut
little stereo-regulation.
Isomerization

CH3 CH3 CH3

CH2=CH-CH XCH2-C+H-CH XCH2-CH2-C+
CH3 CH3 CH3

CH3
[CH2-CH2-C+]n
CH3
 Anionic polymerization

Propagating species is carbanion, initiation is brought about by species

that undergo nucleophilic addition.
-
Nu- + CH2 CHY NuCH2-CHY

For initiation to be successful, the free energy of the initiation step must
be favorable.
If the propagating anion is not very strongly stabilized, a powerful
nucleophile is required as initiator.
If the propagating anion is strongly stabilized, a rather weak nucleophile
will be successful as initiator.
Anionic initiators: 2 classes a) react by addition of a negative ion.
They include organometallic compounds, grignard reagents b) undergo
electron transfer
Initiation -
C4H9Li + CH2 CHY C4H9-CH2-CHY
Li+
Initiation by electron transfer
Works best with styrene and related monomers.
The actual initiating species is derived from an alkalai metal like sodium. An
aromatic compound is required to catalyze the process by accepting an
electron from sodium to form a radical anion salt with Na+ counterion. A
polar solvent is required to stabilize this complex salt. The electron is
subsequently transferred to the monomer to create a new radical anion
which quickly dimerizes.
. .. - +
+ Na [ ] Na
. .. - +
[ ] Na + PhCH=CH2

. +.. - +
[PhCH-CH2] Na
 Propagation

a) In polar solvents where free solvated ions predominates addition of

anion to the monomer takes place
- -
C4H9-CH2-CHY + CH2 CHY C4H9-CH2-CHY-CH2-CHY
Li+ Li+

b) In nonpolar solvents where there is close association

between ions, the mechanism involves initial pi-complex
formation
R-Li RCH2CHY
R-Li + CH2 CHY Li
CH2 CHY
 Termination

Termination by impurities:Any moisture present terminates

propagating carbanions by proton transfer.
Ph
Ph
..- CH -CH + HO -
CH2-C + H 2O 2
H
H

Spontaneous termination: termination by rearrangement of the

propagating ion pair.
Ph Ph
..- + + NaH
CH2-C Na CH=C
H H
Effects of Conditions on Reaction Rates
Because the propagating species caries a counterion, the "tightness" of the ion pair is
strongly affected by the reaction conditions. The tighter the ion pair, the slower the rate
of propagation. This feature is apparent in the following comparison of rates for an
anionic polymerization in solvents of increasing polarity:

Relative Rate
Solvent
Benzene 1
Dioxane 2.5
THF 225
1,2-Dimethoxyethane 1900
Similarly, larger counterions usually form looser ion pairs, so there is an
increase in rate:

Relative
Counterion Rate
Li+ 1
Na+ 3.6
K+ 21.1
Rb+ 22.9
Cs+ 26.1
Acrylates have problems in anionic propagation because of chain transfer
to polymer. The hydrogen atoms adjacent to the ester groups are slightly
acidic, and can be pulled off by the propagating anion. The new anion
thus created can reinitiate, leading to branched polymers.
Methacrylates have a methyl group instead of the hydrogen, so the above
reaction is not a problem. However, both acrylates and methacrylates
suffer from potential reactions at the ester instead of the vinyl group. The
most common circumstance is reaction with the ester two repeat units
back, because the transition state is a six-membered ring (entropically
favorable). The reaction causes a cyclization, and ejects an alkoxide as a
leaving group. Alkoxide is too weak of a nucleophile to reinitiate, so this
process is a termination.
If polymerized anionically and allowed to stand, the end groups of
PMMA are all the rings.
The activation energy of cyclization is greater than that of propagation,
so the former is affected more by temperature than the latter. Simply by
running the reaction at low temperatures, the undesired cyclization
reaction is suppressed, and propagation occurs without problem.
Unfortunately, cooling large reactors is inefficient and costly, so anionic
polymerization of methacrylates is not practiced commercially despite
the desirable characteristics of the polymers produced.
 Group Transfer Polymerization (GTP)

Possible to obtain living polymers at room temperature or above.

Typically an organosilicon compound is used to initiate the
polymerization in solution in the presence of an anionic catalyst
Disadvantages:
Need water free conditions
Expensive process
Used only for acrylates and methacrylates
https://www.slideshare.net/SujoySaha_14/gtp-33678134
 Distinguish between radical and ionic
polymerization

1. Ionic polymerization usually proceeds at lower

temperature, usually below 0ºC. Radical polymerization
almost always proceed at temperature above 50 ºC.
2. Ionic polymerization is sensitive to the changes in the
polarity and solvating ability of the reaction media nad
the counterion effects. Radical polymerization do not
show such effects.

Cationic vs https://www.youtube.com/watch?v=G0EPK42H2-8
Anionic