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Chapter 5 Anionic Polymerization
Chapter 5 Anionic Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
1
Cationic Chain Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
2
Cationic Chain Polymerization
Introduction:
The propagation center is a cation and the counterion is an anion.
Anions encountered in cationic polymerization are usually larger ions
(sulfate, perchlorate).
CH3 O
CH2 C O Cl O
CH3 O
3
Cationic Chain Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
4
Cationic Chain Polymerization
Initiation using protonic acids (Brnsted):
Background: A Brnsted acid is a substance that can donate a proton to
a base.
Protonation of the olefin
CH3 CH3
A H + CH2 C CH3 C A
CH3 CH3
The anion should not be too nucleophilic to avoid recombination with
the carbocation.
CH3 CH3
reactive CH3 C A CH3 C A not reactive
CH3 CH3
5
loose ion pair covalent species
Cationic Chain Polymerization
Initiation using protonic acids (Brnsted):
Hydrogen halides (HF, HCl, HBr) do not initiate polymerization. They
merely undergo addition onto the double bond.
In order to initiate polymerization, the acid should be strong and the
resulting anion should not be too nucleophilic.
Examples:
O O O O
H O Cl O H O S O H O S O H O S O
O F CH3 CF3
6
Cationic Chain Polymerization
Initiation using Lewis acids:
Background: A Lewis acid is any molecule or ion that has an affinity for
an extra pair of electron.
Lewis acids are the most important means to initiate cationic
polymerization.
7
Due to highly electronegative Cl
8
Cationic Chain Polymerization
Initiation using Lewis acids:
A Lewis acid works in combination with either a proton donor (H2O,
ROH, HCl) or a carbocation donor (tert-butyl chloride, trityl chloride).
CH3
CH3 C Cl C Cl
CH3
tert-butyl chloride
trityl chloride
9
Cationic Chain Polymerization
Initiation using Lewis acids:
The proton donor or carbocation donor is called the initiator and the
Lewis acid is referred to as the co-initiator. One speaks of the initiator-
co-initiator complex.
Initiation with boron trifluoride and water
F H F H
K formation of the initiator-
F B + O F B O
co-initiator complex
F H F H
F H CH3 k CH3 F
i
F B O + CH2 C CH3 C F B OH
F H CH3 CH3 F
10
Cationic Chain Polymerization
Initiation using Lewis acids:
Initiation with aluminum chloride and tert-butyl chloride
CH3 CH3
K
CH3 C Cl + AlCl3 CH3 C AlCl4
CH3 CH3
11
Cationic Chain Polymerization
Initiation using Lewis acids:
Generalization
K
I + ZY Y (IZ)
ki
Y (IZ) + M Y-M (IZ)
12
Cationic Chain Polymerization
Initiation using Lewis acids:
Comparison: Initiation with a protonic acid (Brnsted) yields an anion
with the potential of being too nucleophilic. Initiation with a Lewis acid
has the advantage of resulting in the formation of a less nucleophilic
anion. H H
Brnsted protonic acid H F + CH2 C CH3 C F
F F
K
Lewis acid F B + H F F B F H
F F
F H H F
ki
F B F H + CH2 C CH3 C F B F
F F
13
Cationic Chain Polymerization
Initiation using Lewis acids:
In general, the factors that enhance initiation are those that enhance the
association between initiator and co-initiator (K) and the rate of addition
to the monomer (ki).
The activity of the Lewis acid follows the acidity of the lewis acids
AlCl3 > Al(C2H5)Cl2 > Al(C2H5)2Cl > Al(C2H5)3
14
Cationic Chain Polymerization
Stability of the
Initiation The carbocation:
carbocation
CH3 k1 CH3
H3C C Cl H3C C Cl
CH3 CH3
H k2 H
H3C C Cl H3C C Cl
CH3 CH3
k 1 > k2 > k3 > k4
H k3 H
H3C C Cl H3C C Cl
H H
H H
k4
H C Cl H C Cl
H H 15
Cationic Chain Polymerization
Initiation The carbocation:
Initiation with a carbocation must meet a few criteria. The carbocation
must be stable enough so that it can be formed in sufficient quantities.
However the carbocation should not be too stable so that it can still react
with the vinyl monomer.
Primary and secondary carbocations are formed too slowly and in too
small quantities.
16
Cationic Chain Polymerization
Initiation The carbocation:
Initiation with a carbocation must meet a few criteria. The carbocation
must be stable enough so that it can be formed in sufficient quantities.
However the carbocation should not be too stable so that it can still react
with the vinyl monomer.
In summary!
CH3 CH3
K
CH3 C Cl + AlCl3 CH3 C AlCl4 (high yield)
CH3 CH3
CH3 H
H3C C (tert-butyl) CH2 C (styrene)
CH3
CH3 CH3
C (cumyl) (isobutylene)
CH2 C
CH3 CH3
18
Cationic Chain Polymerization
Initiation The carbocation:
CH3 CH3 CH3 CH3
H3C C AlCl4 + CH2 C H3C C CH2 C AlCl4
CH3 CH3 CH3 CH3
CH3 CH3
C AlCl4 + CH2 C C CH2 C AlCl4
CH3 CH3
CH3 CH3
AlCl4 + CH2 C CH2 C AlCl4
CH3 CH3 19
Cationic Chain Polymerization
Initiation The carbocation:
The trityl and cycloheptatriene carbocations are more stable and they can
not initiate the polymerization of isobutylene and styrene. However,
they can initiate the polymerization of more reactive monomers such as
vinyl ethers and paramethoxystyrene.
H2O
SnCl4OH2 H3O SnCl4OH
(not reactive)
initiator/co-initiator
21
Cationic Chain Polymerization
Initiation Other initiator:
Cl2, Br2, and I2 can initiate polymerization in the presence of a Lewis
acid (Al(C2H5)3 or Al(C2H5)2X where X = Cl, Br, I). Only I2 can initiate
polymerization of the more reactive monomers without co-initiator.
(addition) (elimination)
H H I H
I2 + CH2 C ICH2 C I HI + CH C
O O O
CH3 CH3 CH3
H H I2 + CH2 CH OCH3 H H
HI + CH2 C CH3 C I CH3 C CH2 C I
O O O O
CH3 CH3 CH3 CH3
H
CH3 C I The presence of I2
O polarizes the C-I 22
bond
(without I2) CH3 and allows propagation.
Cationic Chain Polymerization
Initiation Electroinitiation:
Oxidation of a polynuclear aromatic compound yields a radical-cation
that can initiate polymerization via electron transfer.
(radical-cation)
H
e H
+ CH2 C + CH2 C
O O
CH3 CH3
H H
Propagation continues from both ends. C H2C CH2 C
O O
H3C CH3
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
24
Cationic Chain Polymerization
Propagation:
After initiation of isobutylene with water and BF3:
kp
CH3 CH3
H CH2 C CH2 C BF3OH
CH3 n+1 CH3
25
Cationic Chain Polymerization
Propagation Rearrangements:
Rearrangements frequently occur in cationic polymerization. Their
probability of occurring depends on the stability of the resulting
carbocation.
H
CH2 C
CH2=CHCH(CH3)2
CH3 C H
CH3
26
Cationic Chain Polymerization
Propagation Rearrangements:
Example #1: Cationic polymerization of 3-methyl-1-butene
H H
kp
R + CH2 C R CH2 C
CH3 C H CH3 C H
CH3 CH3
27
Cationic Chain Polymerization
Stability of the
Initiation The carbocation:
carbocation
CH3 k1 CH3
H3C C Cl H3C C Cl
CH3 CH3
H k2 H
H3C C Cl H3C C Cl
CH3 CH3
k 1 > k2 > k3 > k4
H k3 H
H3C C Cl H3C C Cl
H H
H H
k4
H C Cl H C Cl
H H 28
Cationic Chain Polymerization
Propagation Rearrangements:
Example #1: Cationic polymerization of 3-methyl-1-butene
H H H
kp krearr
R + CH2 C R CH2 C R CH2 C H
CH3 C H CH3 C H CH3 C
CH3 CH3 CH3
(1,2 hydride ion shift)
CH3
R CH2 CH2 C
CH3
H H
R CH C H
H C H
CH3 C
31
CH3
Cationic Chain Polymerization
Propagation Rearrangements:
Example #2: Cationic polymerization of 4-methyl-1-pentene
H H H H
R + CH2 C R CH C R CH C H
H C H H C H H C H
CH3 C H CH3 C H CH3 C H
CH3 CH3 CH3
H H
R CH C H
H C H
CH3 C
32
CH3
Cationic Chain Polymerization
Propagation Rearrangements:
Example #2: Cationic polymerization of 4-methyl-1-pentene
H H H H
R + CH2 C R CH C R CH C H
H C H H C H H C H
CH3 C H CH3 C H CH3 C H
CH3 CH3 CH3
H H
R CH C H
H C H
CH3 C
33
CH3
Cationic Chain Polymerization
Propagation Rearrangements:
Example #2: Cationic polymerization of 4-methyl-1-pentene
H H H H
R + CH2 C R CH C R CH C H
H C H H C H H C H
CH3 C H CH3 C H CH3 C H
CH3 CH3 CH3
CH2
35
Cationic Chain Polymerization
Propagation Rearrangements:
Example #3: Cationic polymerization of b-pinene
H + CH2 CH3
CH3
CH3 CH3 C
CH3
36
Cationic Chain Polymerization
Propagation Rearrangements:
Rearrangements result in polymer backbones that are more complex than
when no rearrangement is taking place. Monomers that yield
carbocations that can be stabilized (for example by resonance like for
styrene or electronic inductive effects like for vinyl ethers) will not
undergo rearrangement. Those that can not be stabilized will undergo
rearrangements (propylene, 1-butene). The cationic polymerization of
propylene and 1-butene results in the formation of short oligomers (Xn <
20) with an irregular structure.
37
Cationic Chain Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
38
Cationic Chain Polymerization
Chain Transfer and Termination:
As for radical chain polymerization, chain transfer reactions occur
frequently in cationic polymerization.
1. Chain transfer to monomer:
A b-proton is transferred from the polymer to the monomer.
H CH3 CH3 k CH3 CH3
tr,M
CH C BF3OH + CH2 C CH2 C + CH3 C BF3OH
H C H CH3 CH2 CH3
H
CH3 CH3
ktr,M
CH C + CH3 C BF3OH
CH3 CH3
39
Cationic Chain Polymerization
Chain Transfer and Termination:
1. Chain transfer to monomer:
A b-proton is transferred from the polymer to the monomer.
Polymerization of styrene and ethyl vinyl ether yields the second
species only.
H H H H H
ktr,M
CH C BF3OH + CH2 C CH C + CH3 C BF3OH
40
Cationic Chain Polymerization
Chain Transfer and Termination:
1. Chain transfer to monomer:
A hydride ion is transferred from the monomer to the growing
carbocation.
41
Cationic Chain Polymerization
Chain Transfer and Termination:
1. Chain transfer to monomer:
Usually: Ea(chain transfer) > Ea(propagation)
The activation energy of chain transfer to monomer is usually larger than
that of propagation. Thus, chain transfer to monomer can be reduced by
working at lower/higher temperatures.
42
Cationic Chain Polymerization
Chain Transfer and Termination:
1. Chain transfer to monomer:
The plain result of chain transfer to the monomer is the termination of a
growing chain and the formation of a new reactive center. Chain transfer
limits the molecular weight but not the rate of polymerization.
ktr , M
CM
kp
43
Cationic Chain Polymerization
Chain Transfer and Termination 2. Spontaneous Termination:
The initiator-co-initiator complex is regenerated during spontaneous
termination.
CH3 CH3
kts
CH2 C BF3OH CH2 C + BF3OH2
H2C H CH2
44
Cationic Chain Polymerization
Chain Transfer and Termination 3. Combination with the counterion:
CH3 CH3
kt
CH2 C BF3OH CH2 C OH + BF3
CH3 CH3
CH3 CH3
kt
CH2 C BCl3OH CH2 C Cl + BCl2OH
CH3 CH3
F Cl
F B OH Cl B OH
45
F Cl
Cationic Chain Polymerization
Chain Transfer and Termination 3. Combination with the counterion:
CH3 CH3
kt
CH2 C Al(CH3)3Cl CH2 C CH3 + Al(CH3)2Cl
CH3 CH3
CH3 CH3
kt
CH2 C Al(C2H5)3Cl CH2 C H + H2C CH2 + Al(C2H5)2Cl
CH3 CH3
All these processes result in the termination of the growing chain and
of the reactive center.
46
Cationic Chain Polymerization
Chain Transfer and Termination Chain Transfer to Polymer:
Intramolecular electrophilic aromatic substitution:
H
CH2 C CH2 C A CH2 CH CH2 + A H
H H CH
(S = XB)
ktr,S
P A + X-B P-B + X-A
48
Cationic Chain Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
49
Cationic Chain Polymerization
Number-Average Degree of Polymerization:
H CH3 CH3 ktr,M CH3 CH3
1. Chain transfer CH C BF3OH + CH2 C CH2 C + CH3 C BF3OH
to Monomer
H C H CH3 CH2 CH3
H
2. Spontaneous
CH3 kts CH3
CH2 C BF3OH CH2 C + BF3OH2
termination
H2C H CH2
CH3 CH3
3. Termination by kt
combination CH2 C BF3OH CH2 C OH + BF3
CH3 CH3
50
Cationic Chain Polymerization
Number-Average Degree of Polymerization:
Since cationic polymerization is more subject to termination than anionic
polymerization, Xn can be estimated from the kinetic chain length (n).
Rp Rp
Xn
Rt Rt Rts Rtr , M Rtr , S
51
Cationic Chain Polymerization
Number-Average Degree of Polymerization:
Rp Rp
Xn
Rt Rt Rts RTr , M Rtr , S
1. Chain transfer to
P A+MP+M A Rtr,M=ktr,M[P+(A-)][M]
monomer:
2. Spontaneous
P AP+A Rts = kts[P+(A-)]
termination:
3. Termination /
P AP+A Rt = kt[P+(A-)]
recombination:
4. Chain transfer to
P A + S P + S-A Rtr,S=ktr,S[P+(A-)][S]
solvent:
P A+MP A
Propagation: Rp=kp [P+(A-)][M]
52
Cationic Chain Polymerization
Number-Average Degree of Polymerization:
Rp Rp
Xn
Rt Rt Rts Rtr , M Rtr , S
1 kt 1 kts 1 [S ]
CM C S
X n k p [M ] k p [M ] [M ]
This equation is similar to the Mayo equation obtained for radical chain
polymerization. 53
Cationic Chain Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
54
Cationic Chain Polymerization
Rate Constants:
One approach consists of determining Rp through a thorough kinetic
analysis of the polymerization.
Ki
Initiation: RA R A Ri = ki[R+A-][M] = kiKi[RA][M]
ki
R A + M RM A ( P A )
Propagation: kp
P A + M P A Rp = kp[P+A-][M]
Termination:
kt
P A P-A Rt = kt[P+A-]
55
Cationic Chain Polymerization
Rate Constants:
The steady-state assumption can be applied to estimate [P+A-]:
Ri = ki[R+A-][M] = kiKi[RA][M]
Rp = kp[P+A-][M]
Rt = kt[P+A-]
-ki K i ki K i
Ri = Rt [P A ] [ RA][ M ] Rp k p [ RA][ M ]2
kt kt
Rp scales as [RA]1 and [M]2. This result is different from radical chain
polymerization where Rp increases as [I]1/2 and [M]1.
56
Cationic Chain Polymerization
Rate Constants:
Unfortunately, the steady-state assumption is not valid in many, if not
most, cationic polymerizations! Cationic polymerizations proceed so
quickly that steady-state conditions are never achieved. Some of these
polymerizations are essentially complete in a matter of seconds or
minutes.
An estimate of kp for cationic polymerization requires that [P+A-] be
measured. As in anionic polymerization, this is complicated by the
presence of two propagating species: the ion pairs and the free ions.
57
Cationic Chain Polymerization
Rate Constants:
Rp k papp[M ] [ P A- ] [ P ] k p [M ][ P A- ] k p [M ][ P ]
with
k p [ P A- ] k p [ P ] [ P ][ A- ]
k papp and K
-
[P A ] [P ]
[ P A- ]
Rp k papp[M ] [ P A- ] [ P ] k p [M ][ P A- ] k p [M ][ P ]
with
k p [ P A- ] k p [ P ] [ P ][ A- ]
k papp and K
-
[P A ] [P ]
[ P A- ]
As for anionic polymerization, addition of a salt to the polymerization
mixture shifts the equilibrium towards the ion pairs, which slows down
the reaction and yields a smaller kp value. Conducting several
polymerization reaction with different salt concentrations would yield
k p , k p . In practice, this procedure which is commonly used for anionic
polymerization has not been much applied to cationic polymerization.
59
Cationic Chain Polymerization
Rate Constants Comparison of Rate Constants:
Monomer k (10-4 L.mol-1.s-1) k (10-4 L.mol-1.s-1)
p p
CH2
CH 120 10
(styrene)
CH2
10
H3CO CH 36 4
(p-methoxystyrene)
CH2 CH
N
60 5
60
(N-vinylcarbazole)
Cationic Chain Polymerization
Rate Constants Comparison of Rate Constants:
In general, k p is one order of magnitude larger than k p . The difference
between k p and k p ( 10) is less than between k p- and k p ( 1,000)
observed for anionic polymerization. This effect is due to the larger size
of the counterion in cationic polymerization.
As for anionic polymerization, cationic polymerization proceeds faster
than radical polymerization due to a lower rate of termination and a
higher concentration of propagating species.
61
Cationic Chain Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
62
Cationic Chain Polymerization
Effect of Solvent:
Since k p is one order of magnitude larger than k p , any effect
app
increasing the concentration of the free ions will increase k p . Polar
solvents increase dissociation which results in increased Rp (or k papp).
63
Cationic Chain Polymerization
Effect of the Counterion:
Since the counterions are large, there are less electrostatic interactions
between the propagating carbocation and the counterion (loose ion
pairs). There is little effect of the counterion on the reactivity of the ion
pairs. Of course, there is no effect of the counterion on the reactivity of
the free ions.
64
Cationic Chain Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
65
Cationic Chain Polymerization CH3
Industrial Cationic Polymerization: CH2 C
Isobutylene-based polymers are very important commercially. CH3
Very low molecular weight: (Mn < 3000, 80% isobutylene and 20% 1-
butene) These polymers are used as adhesives, sealants, lubricants,
plasticizers, and motor oil additives. They are called polybutenes.
Low molecular weight: (Mv < 5104) Polyisobutylenes are either
viscous liquids or tacky solids which are used for sealant applications.
High molecular weight: (Mv > 105) These polyisobutylenes are rubbery
solids that are produced by conducting the polymerization at low
temperature with a chain transfer agent to control the molecular weight.
Butyl Rubber: It is a copolymer of isobutylene and small amounts of
isoprene (0.5 2.5%). Incorporation of isoprene enables crosslinking.
Butyl rubber remains flexible down to 50 oC (no crystallization like
polyisoprene). The material does not contain many unsaturated double66
bonds and exhibits good resistance against aging, moisture, chemicals.
Cationic Chain Polymerization CH3
Industrial Cationic Polymerization: CH2 C
Isobutylene-based polymers are very important commercially. CH3
Chewing Gum: It is made by copolymerizing isobutylene and small
amounts of isoprene. It is clear and odorless, chewable even at low
temperatures, absorb large amount of fillers and additives, resistant to
oxidation, and available in a wide variety of grades that conform with the
U.S. Food and Drug Administration's (FDA) requirements for food uses.
67
Cationic Chain Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
68
Cationic Chain Polymerization
Differences between Radical, Anionic, and Cationic Polymerizations:
Temperature: Ionic polymerizations are conducted at temperatures lower
than 0 oC. Radical polymerizations are carried out at temperatures
larger than 0 oC.
Solvent polarity: It affects ionic polymerizations much more than radical
polymerizations.
Protic solvents: protic solvents (water, alcohol) terminate ionic
polymerization, but not affect radical polymerization.
69
Radical scavenger: A radical scavenger will stop a radical
polymerization but not an ionic polymerization.
Example of radical scavenger 2,2-diphenyl-1-picrylhydrazyl
(DPPH)
(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl or (2,2,6,6-
tetramethylpiperidin-1-yl)oxidanyl, (TEMPO)
70