Chapter 7.

Ionic and Living Polymerizations

Contents
 7.1 Introduction ……………………………………………………………… 2
 7.2. Cationic Polymerization ………………………………………………… 6
7.2.1. Cationic Initiators ………………………………………………………… 6
7.2.2. Mechanism and Reactivity in Cationic Polymerization ………………… 10
7.2.3. Chain Transfer and Termination in Cationic Polymerization …………… 12
7.2.4. Kinetics of Cationic Polymerization ……………………………………… 15
7.2.5. Living Cationic Polymerization ………………………………………… 17
7.2.6. Stereochemistry of Cationic Polymerization …………………………… 19
 7.3. Anionic Polymerization ……………………………………………… 34
7.3.1. Anionic Initiators ………………………………………………………… 34
7.3.2. Mechanism and Kinetics in Anionic Polymerization …………………… 40
7.3.3. Anionic Copolymerization ……………………………………………… 48
 7.4. Controlled (Living) Radical Polymerization ……….…………………... 50 1
 7.1. Introduction
Ionic polymerizability of vinyl monomers

2
Electron-releasing substituents for cationic polymerization

Electron-withdrawing substituents for anionic polymerization

3
4
Ionic polymerization
 Counterions are present to preserve electrical neutrality.
 The mechanism is strongly influenced by the counterions.
 Versatile in the steric and MW controls.
 Monomers must contain substituent groups capable of stabilizing
carbocations or carbanions.

 An organic salt A+B-, a continuous spectrum of ionicities (“Winstein

spectrum”) can be depicted as:

5
 7.2. Cationic Polymerization

7.2.1. Cationic Initiators

 (1) Protonic acids (recall that electrophilic addition of alkene)

H2SO4, H3PO4
 (2) Lewis acids: initiators and coinitiators
Metal halides: BF3, AlCl3, SnCl4, PCl5, SbCl5, TiCl4
Organometallic derivatives: RAlCl2, R2AlCl, R3Al

6
Most or perhaps all of the Lewis acids are seldom effective alone as
initiators or catalysts; they are used in conjunction with a second
compound, called a ‘co-catalyst’, which very often is water or some
other proton donor (protogen) such as hydrogen halide, alcohol,
and carboxylic acid, or a carbocation donor (cationogen) such as t-
butyl chloride and triphenylmethyl chloride. On reaction with the
Lewis acid, they form a catalyst-cocatalyst complex that initiates
polymerization.

7
Many polymerizations exhibit a maximum polymerization rate at some
ratio of initiator to coinitiator.

8
 (3) Autoionization: for very reactive Lewis acids

 (4) Other initiators

 (5) Other initiation mechanisms

Photoinitiation; Electroinitiation; Ionizing radiation
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7.2.2. Mechanism and Reactivity in Cationic Polymerization
 (1) In carbocationic initiation, addition of the E+ species follows the
extended Markovnikov’s rule, that is, the most stable carbocation
intermediate is formed. Therefore, the rate of addition of aliphatic
monomers is in the order:

Reactivity of para-substituted styrene

 (2) Vinyl ethers are particularly reactive, why?

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 (3) General considerations of chain propagation

 (4) Solvent effects

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7.2.3. Chain Transfer and Termination in Cationic Polymerization

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 (1) Chain transfer to monomer is so common in cationic polymerization.
How to circumvent it?

 (2) Transfer reaction as a route to prepare telechelic polymers

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 (3) Termination reactions are harder to define in cationic processes
because they are easy to confuse with chain transfer

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7.2.4. Kinetics of Cationic Polymerization: Simplified
Kinetic Scheme

We have ignored the presence of

free solvated ions and ion pairs of
various degrees of closeness
occurring in equilibria.

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7.2.5. Living Cationic Polymerization
 Living polymerizations are polymerizations without chain-breaking
reactions.

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 General requirements for LCP
By choosing the initiator, coinitiator, and other components of a reaction so that
there is no nucleophile present that can irreversibly terminate the propagating
cationic species. Basic components also need to be avoided to minimize β-proton
transfer.
The major approach to extending the lifetime of propagating species involves
reversible conversion of the active centers to dormant species such as covalent
esters or halides by using initiation systems with Lewis acids that supply an
appropriate nucleophilic counterion.

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7.2.6. Stereochemistry of Cationic Polymerization
 Conformation vs. Configuration
Conformation – the different orientations of atoms and substituents in a
molecule that result from rotations around single bonds.
– eg. for polymers, the fully extended planar zigzag, random coil, helical,
and folded-chain arrangements
– Conformational isomers can be interconverted one into the other by bond
rotations.
Configurational isomer – differences in the spatial arrangements of their
atoms and substituents in a manner such that they can be interconverted
only by breaking and reforming primary chemical bonds.
 Stereoregular Polymerization
Cationic Initiation of Vinyl Ethers
OR OR OR OR
BF3.Et2O
O
Propane
CH2 - 80-60 C
H3C
CH3
19
Schildknecht et al. Ind. Eng. Chem. 39, 180, (1947)
20
Atactic – the R groups on successive stereocenters are randomly distributed on
the two sides.
Isodiotactic – all the R groups are on the same side, and the stereocenter in each
repeating unit in the polymer chain has the same configuration.
Syndiotactic – the R groups located alternately on the opposite sides, and the
configurations of the stereocenters alternate from one repeating unit to the next. 21
 Stereochemistry of SN1

The SN1 reaction produces mixtures of enantiomers. There is usually more

inversion than retention of configuration.

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 Stereochemistry of vinyl polymer
Definitions and notation
[-CH2-CXY-]n

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The spectrum of the CXY group

 The chemical shifts of nuclei

in the CXY group will depend
on the tacicity of its nearest
neighbors.
Isotactic placement corresponds to
meso or m-placement for a pair of
consecutive stereocenters.
Syndiotactic placement corresponds to
racemo (for racemic) or r-placement for
a pair of consecutive stereocenters.

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Dyad tacticity is defined as the fractions of pairs of adjacent repeating units that are
isotactic or syndiotactic to one another.
- The isotactic and syndiotactic dyads (XV) are usually referred to as meso and
racemic dyads.
- The horizontal line in XV represents a segment of the polyme rchain, and each
vertical line represents the configuration at the stereocenter in a repeating unit.
- The fractions of isotactic and syndiotactic dyads are referred to as (m) and (r)
Triad tacticity describes isotactic, syndiotactic, and heterotactic triads (XVI) whose
fractions are designated as (mm), (rr), and (mr), respectively.

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Example
Chain segment XVII has a total of 9 repeating units but only 8 dyads and 7 triads.
There are 6 meso dyads and 2 racemic dyads; (m) = ¾, (r) = ¼
There are 4 isotactic, 2 heterotactic, and 1 syndiotactic triads;
(mm) = 4/7, (mr) = 2/7, (rr) = 1/7

Correlation between dyads and triads

Atatic polymer – (m) = (r) = 0.5, (mm) = (rr) = 0.25, (mr) = 0.5
Isotactic polymer – (m) = (mm) = 1
Syndiotactic polymer – (r) = (rr) = 1
Random tactic polymer
– Isotacticity predominates when (m) >0.5 and (mm) > 0.25
– Syndiotacticity predominates when (r) > 0.5 and (rr) > 0.25.
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 NMR spectra of stereoregular polymers

 PMMA

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 PVC

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 The assignment given is based on statistical arguments

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7.2.7. Commercial Applications of Cationic Polymerization
Butyl rubber (BR) is a copolymer of isobutylene with small amounts of
isoprene produced by aluminum chloride initiated polymerization.

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 7.3. Anionic Polymerization

7.3.1. Anionic Initiators

 (1) Initiation is brought about by species that undergo nucleophilic
addition to monomer
 (2) The strength of the base necessary to initiate polymerization depends
on monomer structures
 (3) Two basic types of initiation
(i) Nucleophilic initiators
n-C4H9Li, C6H5CH2Li, NaNH2, KNH2, C6H5CH2Na, CH3ONa, and EtMgBr.

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Super glue (cyanoacrylates) is up there with Velcro as materials we have always
taken for granted without really acknowledging someone had to be clever
enough to invent them in the first place. In the case of super glue that person was
Harry W. Coover, and he has just passed away at the ripe old age of 94.
His fast-acting and super-strong adhesive was invented in 1942 as a side effect
of another project to create transparent plastic gun sights. The sights didn’t
work out because the material created stuck everything together, but the
adhesive that came out of those experiments was eventually sold as a super glue
called Eastman 910.
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Curing Mechanism
When confined in a thin film between two surfaces, cyanoacrylate adhesives cure rapidly at
room temperature to form rigid thermoplastics with excellent adhesion to most substrates.
Cyanoacrylates typically reach handling strength within one minute at room temperature and
achieve full strength in 24 hours.
Cyanoacrylate adhesives undergo anionic polymerization in the presence of a weak base,
such as water, and are stabilized through the addition of a weak acid. An essential function of
the stabilizer is to prevent polymerization in the container, which is usually made of
polyethylene.
When the adhesive contacts a slightly alkaline surface, trace amounts of adsorbed water or
hydroxide ions (OH-) that are present on the substrate’s surface neutralize the acidic
stabilizer in the adhesive, resulting in rapid polymerization.
In general, ambient humidity in the air and on the bonding surface is sufficient to initiate
curing within a few seconds. Therefore, parts must be joined quickly. The open time is
dependent on the grade of adhesive, the ambient temperature and relative humidity, and the
nature of the substrate surface (pH and amount of adsorbed water).
Optimal bonding conditions are when the ambient relative humidity is between 40% and 60%.
Lower humidity slows cure, high humidity accelerates it, but could lead to lower bond
strength. To achieve the fastest cure, a very thin bond line is desirable. The cyanoacrylate
adhesive need only be applied to one surface.
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(ii) Initiation by electron transfer
Alkali metals can donate electrons to the double bonds yielding anion
radicals and positively charged, alkali-metal counterions. This may result
either from direct attack of the monomer on the alkali metal, or from attack
on the metal through an intermediate compound such as naphthalene. Both
result in bifunctional initiation, that is, formation of species with two
carbanionic ends

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 anion radical

dimerization

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7.3.2. Mechanism and Kinetics in Anionic Polymerization
 (1) Initiation by anion vs. initiation by electron transfer

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 (2) Kinetics for living anionic polymerization

Following the work of Michael Szwarc in the mid-1950s, it became known that
under carefully controlled conditions carbanionic living polymers could be formed
using electron transfer initiation. Because the growing chains in anionic
polymerization, carrying negative charges, cannot react with each other, there is
no compulsory chain termination through recombination. In polymerization
systems, especially of nonpolar monomers such as styrene and 1,3-butadiene in
perfectly dry inert solvents such as benzene and tetrahydrofuran, initiated by
organometallic compounds, termination or transfer is virtually nonexistent and
active chain ends can thus have indefinite
lifetimes. Such systems are referred to as living polymers. Propagation continues
till 100% conversion of the monomer is reached, while the propagating anionic
centers remain intact and
capable of further propagation if more monomer (either same or different) is
added.

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Nature, 1956, 1169

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 (3) Polymerization with simultaneous propagation and chain transfer

Polymerization follows
in a manner similar to
free-radical polymerization.

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 (4) Chain transfer reactions

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 (5) The factors in propagation rate
(i) Association between counterion and terminal carbanion

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(ii) Chemical structure of the monomer

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7.3.3. Anionic Copolymerization

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 7.4. Controlled/"Living" Radical Polymerization

Common Mechanisms
 ATRP: atom transfer (radical) polymerization
 NMP or SFRP: nitroxide mediated polymerization or stable free
polymerization
 RAFT: reversible addition transfer or degenerative transfer or catalytic
chain transfer

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POLIMERY 2014, 59, nr 1

Macromolecules 2012, 45, 4015−4039 52

Macromolecules 1995 , 28, 1721-1723
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Macromolecules 2017, 50, 2603−2614 54
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