Anionic Polymerization

Concepts
General Mechanism
Initiation
In Nu-E+

Nu
R
Nu- +
R

Propagation

Nu
Nu Nu n R
R
R + R R
R R
Reaction is facilitated by electron withdrawing groups, e.g. :

NO2, CN, CO2R, CH=CH2, Aryl

Concepts Anionic Polymerization

General Mechanism
Termination

E
Nu n R E+ n
Nu R
R R
R R

H
E+ E n R
E n R
β-elim R
R R
R

Chemistry Anionic Polymerization

Initiators
1. Nucleophilic: Strength of nucleophilic initiater depends on monomer

n-C4H9Li, ArylMgBr, RO-, CN-, NaNH2, LiNR2, RNH2

- R Li+
Li+ +
R

R
+
R Li+
Li +
R R

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 Chemistry Anionic Polymerization
Initiators

2. Electron Transfer

.+ .+
In + M In + M

Na+ - Na+
+ Na =

Anionic Polymerization
Chemistry

-
-
- Na+
+ +

greenish-blue red
dimerize

- -

Anionic Polymerization
Chemistry
Propagation
Monomer Structure: anion stabilized by electron withdrawing group

R
OMe OH
O O

Rates

CN
OMe
O

CN CN

Rate determined by both sterics and polar factors. Trend is not the same as free radical

2
 Chemistry Anionic Polymerization
Ion Structure: Species

B A B- A+

covalent contact
ion pair

-
B
A+
B
- B-
A+
-
B

Aggregate
Ions

- +
B A
B- A
+

free ions solvent separated

ion pair

Anionic Polymerization
Chemistry
Counterions

Counterion Rate in Dioxane

(less polar)
Li+ 0.94
Na+ 3.4
K+ 19.8
Rb+ 21.5
Cs+ 24.5
Solvation not important in dioxane, Reactivity is that with the weakest bond
therefore, the ion pair with the highest (releases more highly active free ions)

Anionic Polymerization
Chemistry
Solvent Effects

Solvent Dielectric kpapp

Constant
Benzene 2.2 2

Dioxane 2.2 5

THF 7.6 550

1,2 5.5 3800

Dimethoxyethane

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Chemistry Anionic Polymerization
Termination
1. Hydride Transfer

H H

Na+ or K+
+ NaH

but not Li+

2. Chain Transfer or Protonating Impurities

H H

+
H
Li
+ H+Z-
(e.g. H2O)

Anionic Polymerization
Chemistry

Termination

3. Intramolecular

O O
OMe
COOMe
COOMe

O OMe O OMe

Anionic Polymerization
Kinetics
Dissociation: e.g. free ions

Nu- E+ Nu- + E+ Rd = kd [Nu- E+]

Initiation Ri = ki [M] [Nu-]

[Nu-] [E+] K [Nu- E+]

K = [Nu-] =
[Nu E ] - + [E+]

ki K [Nu- E+] [M]

Ri =
[E+]

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 Anionic Polymerization
Kinetics

Propagation [NuM-] + [M] [NuMM-]

Rp = kp [M] [NuM-]

Termination: [NuM-] + [H2O] [NuMH] + OH-

Rt = kt [H2O] [NuM-]

Steady state approx:

ki K [Nu- E+] [M]
Ri = = Rt = kt [H2O] [NuM-]
[E+]

ki K [Nu- E+] [M]

[NuM-] =
kt [H2O] [E+]

Anionic Polymerization
Kinetics
Rp = kp [M] [NuM-]

kp ki K [Nu- E+] [M]2

Rp =
kt [H2O] [E+]

Degree of Polymerization DP = Rp/Rt = Rp/Ri

kp ki K [Nu- E+] [M]2 ki K [Nu- E+] [M]

= +
kt [H2O] [E ] [E+]

kp [M]
=
ki [H2O]

Note: = [M] / [I] or 2[M] / [I]

Anionic Polymerization
Telechelic Transformations

Block Copolymers

B C
AAA- AAABBB- AAABBBCCC-

Reverse Transformation

COCl2 O
AAA- AAA Cl
AgSbF6

B
AAABBB+SbF6- AAA+SbF6-

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 Anionic Polymerization
Telechelic Transformations
Synthetic Transformations
AAA

Br
O
1.
AAA- AAA OH
2. H2O
1. CO2
2. H2O
O
AAA OH

Coupling Reactions

An
AAA- + SiCl4 AnSi An
An

Anionic Polymerization
Carbonyl Polymerization

H H Nu
Initiation Nu-E+ +
O O-
E+
Propagation
Nu H H Nu Nu
+ O n O- E+
-
O O- E+ O
O O
E+

Termination
Nu Nu
O O n O- E+ + H2O O O n OH + E+OH-

End Capping
O O
Nu O Nu O
O O n OH O On O

Anionic Polymerization
Other Anionic Polymerizations

R H R, I, C
C n + n
H H R R

R
A N
R N C O n
O

R
R, I, C
R C CH n

I, R R
R C N C
N n

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 Anionic Polymerization
Stereochemical Considerations
Diene Polymerization: e.g. Polyisoprene (synthetic rubber)

+ nbuLi + + +

1,4 cis 1,4 trans 1,2 3,4

Counterion Solvent 1,4 cis 1,4 trans 1,2 3,4

Li Pentane 94 --- --- 6

Li Pentane/THF 0 25 10 65

Li THF --- --- 25 75

Li Et2O --- 50 5 45

Na pentane small 40 7 53

K pentane small 55 7 38

Anionic Polymerization
Stereochemical Considerations

Li+
Li+ Li+

+
Li+
Li+

Li+

Note: Na+ or K+ not effective—too large to promote cyclic transition state