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Introduction
Reaction mechanism of anionic Anionic addition polymerization is an ionic polymerization of vinyl monomers
polymerization reaction and examples. and can be categorized as a chain polymerization initiated with nucleophilic
reagents, such as organolithiums, Grignard reagents, and metal alkoxides.

Anionic addition polymerization proceeds with the growing chain end carrying
negative charge and counter cation.

The typical monomers capable of anionic addition polymerization involve vinyl

By monomers having electron-withdrawing groups, such as methyl methacrylate,
acrylonitrile, and 2-vinylpyridine, as well as conjugated hydrocarbon
Chayan Anand monomers, such as styrene and 1,3-butadiene.

Anionic Polymerization Mechanism 2. Propagation

In the propagation reaction of anionic addition polymerization, the propagating carbanion
1. Initiation repeatedly attacks the vinyl group of monomer to regenerate the propagating carbanion of
the same structure.
The anionic addition polymerization is generally initiated with nucleophilic initiators, and
The propagation rate in the anionic polymerization is remarkably affected by the polarity of
vinyl monomers act as electrophiles in the initiation and propagation reactions.
the polymerization solvent, since the aggregation state of the propagating carbanion largely
Most reactive initiators consists of alkali metals, alkali-metal naphthalenides, and varies with the solvation.
organolithium (RLi) (or sodium and potassium) (RNa and RK) compounds, such as n- and
The rate of polymerization tends to increase, when the equilibrium shifts by adding the
sec-butyllithium (BuLi) and cumylpotassium.
polar solvents to dissociate the propagating species.(counter ions are solvated )
The reactivity of monomer depends upon the stability of the anion forms after initiation
reaction. The reaction also depends upon the initiation ability of initiators.

Propagation of styrene with sodium naphthalenide[1]

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3. Termination
The propagating chain ends carrying negative charges are usually stable, since the bimolecular
Anionic Ring-Opening Polymerization
coupling reaction popular in the radical polymerization is prohibited because of the repulsion of the
negative charge of terminals. In addition, the -elimination popular in the cationic polymerization of Lactams (cyclic amides)[2]
hardly occurs, since the hydride (H) with a negative charge is difficult to form compared to the
proton (H+) with a positive charge.[2,4]
This means that the termination and transfer polymerization, living polymerization, is often
attained because of the stability of the propagating carbanion.
Caprolactum Nylon 6 or polycaprolactam
In the anionic polymerization, termination of the propagating carbanion takes place with various
acidic compounds, such as water, or electrophilic reagents, such as carbon dioxide and alkyl
halides.
In the typical termination, the propagating carbanion-derived vinyl monomers easily abstract the
hydrogen of acidic compounds, such as water, alcohol, and even amine, to result in the formation of
terminated polymer and more stable conjugated bases, hydroxide, alkoxides, and amide anion. If
the resulting conjugated base acts as a new initiator, the reaction can be defined as the chain
transfer reaction.[1,4]

Poly(isoprene-b-styrene-b-ethylene
CONCLUSION
oxide) (ISO)[3]
ADVANTAGES DISADVANTAGES

1. Very stable propagating anionic 1.The reactions are also very

species are (even after sensitive to impurities during
monomers are fully consumed). reaction Generally not compatible
with glycols, oxides, amines, etc.
2. It allows a very straightforward Any labile proton source in the
synthesis of block copolymers. monomer terminates reaction.
Since monomer batches are
completely consumed, one can 2.Low temperature is needed to
simply add a different perform living polymerization and
comonomer to the ensure termination and transfer by
polymerization mixture.
mildly polar solvent.

3. Highly mono-disperse product is 3.Cumbersome working conditions

obtained. in terms of apparatus, reaction
conditions, solvent selection.

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References

1. Anionic Addition Polymerization (Fundamental) Takashi Ishizone* and Raita Goseki

2. http://taner.balikesir.edu.tr/dersler/polimer_kimyasi/ekler/polimersorulari/Chapter%204.
pdf
3. https://www.researchgate.net/publication/310510315_Polymerization
4. Haddleton, D.M., Kukulj, D., Duncalf, D.J., Heming, A.M. and Shooter, A.J., 1998.
Low-temperature living radical polymerization (atom transfer polymerization) of
methyl methacrylate mediated by copper (I) N-alkyl-2-pyridylmethanimine
complexes. Macromolecules, 31(16), pp.5201-5205