Spring 2008

Chap 10. Non-Radical Addition Polymerization

Anionic Polymerization -the growing chain end bears a negative charge

The mechanism of anionic polymerization is a kind of repetitive conjugate addition reaction .

(the "Michael reaction" in organic chemistry)

Cationic Polymerization -the growing chain end bears a positive charge

The mechanism of cationic polymerization is a kind of repetitive alkylation reaction.

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 Spring 2008

Anionic Polymerization

General Scheme

Initiation:

B-Z + CH2=CHX B-CH2-CH- Z+

X
Propagation:

M - Z+ + M MM- Z+

Termination:
M- Z+ + HT MH + ZT

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 Spring 2008

Anionic Polymerization

Styrene Polymerization
Initiation:

CH3CH2 CH Li + CH2 CH CH3CH2 CH CH2 CH Li

CH3 CH3

Propagation:

CH2 CH Li + CH2 CH CH2 CH CH2 CH Li

Termination:

CH2 CH Li + H OH CH2 CH2 + Li OH

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 Spring 2008

Anionic Polymerization
Characteristics of an Ideal Anionic Polymerization
 Negative centers repel one another and thus termination by recombination is not possible. An ideal polymerization is “living”, which does not terminate until a terminator is added.
 Initiation is normally very fast relative to propagation and all chains grow simultaneously. This leads to polymers with low polydispersity or monodispersity.
 Theoretically:

 The rate of polymerization for methacrylates and styrenes is high even at -78 oC. This is partly for the high concentration of the anion centers.
 The degree of polymerization

 K=1 or 2 depending on initiator used.

Mw 1
 1
Mn xn

K M 0
xn 
I 0

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 Spring 2008

Anionic Polymerization
Initiation by Electron Transfer
-.
THF
+ K K+
-78 oC

-. . - +
CH2 CH CH2 CH K
K+ + +

. -
CH2 CH K + + - -
K CH CH2 CH2 CH K +
2

• Polymerization mostly done in THF and not nonpolar solvents like

cyclohexane or benzene for the solubility the complex in THF.
• The degree of polymerization is given by

2M 0
xn 
I 0
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 Spring 2008

Anionic Polymerization
Initiation by Nucleophilic Attack

CH3(CH2)2 CH2 Li +
CH2 CH THF CH3(CH2)4 CH Li +
+
-78 oC

CH3 CH3
THF
N Li + CH2 C N CH2 C Li +
-78 oC
COOCH3 COOCH3

• Polymerization can be done in both polar and nonpolar solvents.

• The degree of polymerization is given by

xn 
M 0
I 0
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 Spring 2008

Anionic Polymerization
Initiation by Living Polymer
CH3 CH3
THF
CH2 CH Li + + CH2 C CH2 CH CH2 C Li +
COOCH3 -78
oC
COOCH3

But not
CH3
CH2 C Li + + CH2 CH
COOCH3

Because the starting anion has to be a stronger Lewis base than the
resulting anion.

xn 
M 0
I 0
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 Spring 2008

Anionic Polymerization
Propagation
- - +
M Z M Z+ M Z M
-
+ Z
+

Covalent Contact Ion Solvent Separated Free ions

Bond Pair Ion Pair

Solvent polarity increases

kP increases

Polymer tacticity decreases

• Kp can vary by orders of magnitude.

• The polydispersity remains low because the rate of inter-conversion

between the different forms is much faster than the polymerization.

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 Spring 2008

Anionic Polymerization
Termination
By proton

- H+
M Z+ MH + Z +
By CO2

CO2
- -
M Z+ MCOO Z +

By using a limiting amount of 1,2-dibromoethane

- CH2Br CH2Br
2 M Z+ M M

K=2

By using a much excess of 1,2-dibromoethane

- CH2Br CH2Br
M Z+ M Br

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 Spring 2008

Anionic Polymerization
(1) proton donor H2O or ethanol
Strong base is not enough for initiation.
H
CH2 C :- + H2O -
CH2 CH2 + OH

H2O Ctr,s=10
Strong base is not
H2O low MW polymer
enough for initiation.
No living polymer
(2) H

CH 2 C:- + C 2H 5 OH CH 2 CH 2 + C 2H 5 O -

Ctr,s=10-3 (small chain transfer constant)

EtOH high MW product

ethoxide no longer living.
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 Spring 2008

Anionic Polymerization
(3) Termination can occurred by hydride elimination without impurities.
CH2 CH CH2 CH:-Na+
CH2 CH CH CH
a)

+ -
+ Na H :
b) anionic species(active center) react with chain ends to form inactive
allylic anion.
. .-
CH2 CH + CH2 CH CH CH

1,3 diphenylallyl anion is

CH2 CH2 ..- very unreactive, highly
+ CH2 CH CH CH
resonance stabilized

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 Spring 2008

Anionic Polymerization
Termination of polar monomer

CH3 O CH3 O
- +
CH2 C C OCH3 + - +
R Li CH2 C C R + CH3O Li

In this case, although the initiator or active center attacks the monomer, that results the
non-polymerization.

CH3 CH3
CH2 C:- Li+ + CH2 C
COOCH3 COOCH3

CH3 O CH3
+ -
CH2 C C C CH2 + Li CH3O
COOCH3

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 Spring 2008

Anionic Polymerization
Backbiting or intramolecular reaction

CH3 O O
O CH3
C¨ CH3 C
CH2 C - C CH2 C C -
COOCH3 COOCH3 + CH3O

CH3 COOCH3 CH3 COOCH3

Cyclic trimer at the end of

chain
4) Hugginson-Wooding System
J.Chem. Soc. 1952
Polymerization of styrene conducted in liq. NH3 at bp -33C

(1) reaction rate ↑ as [I] and [M]2

I=K+NH2- rate ↑ as [NH2-] ↑ but as [K+] ↓
(2) MW  [K+] and [NH2-]
(3) Polymer is formed without unsaturation.

Hanyang Univ.
 Spring 2008

Anionic Polymerization
Initiation step

k
KNH2 K NH2 Dissociation of initiator

[K  ][NH 2  ]
k
[KNH 2 ]

H
NH 2 + CH CH 2 k1
H 2N CH 2 -
C:

 k i K[M][KNH 2 ] 
R i  k i [N H 2 ][M]  
 If [K+] , then Ri 
[K ]

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 Spring 2008

Anionic Polymerization
Propagation
H2N Mn- + M
kp
H2N Mn . M- R p  k p [M  ][M]
Termination
Occurs by chain transfer
H H
ktr,s
H2N CH2 CH CH2 C:- + NH3 H2N CH2 CH CH2 C + : NH2
-

n n
Overall Rate using Steady state assumption. (R iRt). Rtr=ktr,s[M-][NH3+]

K  ki  k p [ M ]2 [ KNH 2 ] ki  k p [ M ]2 [ H 2 N  ]
Rp  

ktr , s [ K ][ NH 3 ] ktr , s [ NH 3 ]
1 1
Ri  ki K [ M ][ KNH 2 ]
2 2

1 1
2
ki K k p [ M ] [ KNH 2 ]
2 2
If KCl is added  Rp decreases
Rp 
ktr , s [ NH 3 ] [K+]=[NH2-]
Hanyang Univ.
 Spring 2008

Anionic Polymerization
In dehydrate state,
k p [M ] [M ]
Xn  
ktr ,s [ NH 3 ] Cs [ NH 3 ]

Chain transfer constant for solvent

Activation energy for Xn

E xn  E p  E tr  4kcal / mole
 temp  DP n  Rate
overall rate
E R  E i  E p  E tr  9kcal / mole

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 Spring 2008

Anionic Polymerization
In Flory
O
RONa + nCH2 CH2 RO(CH2CH2O) n- 1 CH2CH2O-Na+

If there is no termination rxn, the narrow MW distribution can be obtained.

Mw 1 Mw
 1  if X n   1
Mn Xn Mn
5) Base Initiated Polymerization

- a strong nucleophile is required as the initiator

NO 2 > C O > SO 2 > CO 2  CN > SO > C 2H 5

 CH CH 2 >>> CH 3

Hanyang Univ.
 Spring 2008

Anionic Polymerization
6) Practical Comments
purity import!

If we use metal as an initiator, the propagation rate is fast.

7) Propagation Kinetics
Comparing to the radical polymerization, the propagation doesn’t occur too fast

R p  k p [ M  ][ M ]
For most of the living polymers conc. of anion = conc. of initiator
[M:-] = [I]
[M] = is about 10-9 to 10-7 molar
[M:-] = 10-3 to 10-2 molar
kp for free radical case is 5103 l/molesec
Kp : depends on solvent and counter ion
Counter ion and active center can be separated by changing the solvent
 then reaction rate increases
Hanyang Univ.
 Spring 2008

Anionic Polymerization
(1) Evaluation of Individual Propagation Rate Constants

R p  k p  [P  ][M]  k p  [P  (C  )][M]

Propagation rate constant for free ion and ion pair.

[P-]: conc. of free ion
[P-(C+)]: conc. of ion pair


app k p [ P  ]  k  [ P  (C  )] app
kp  
R p  k p [ M  ][ M ]
[M ]
at Eq. P  (C  ) K P  C 

1 [ P  (C  )]

K [ P  ][C  ]
if more ions have been added,
[ P  ]  [C  ]
1
  
[ P ]  ( K [ P (C )]) 2

Hanyang Univ.
 Spring 2008

Anionic Polymerization
* How to measure kp, kp, K ?

C0
log
C

[M ]

slope  k papp.

k app
1
 
slope  ( k  k ) K
p p
2

intercept  k p

[M  ] 2
Hanyang Univ.
 Spring 2008

Anionic Polymerization
A salt that must be soluble in THF with common ion to gegen ion is added to reaction mixture
 K[M  ]
[P ]  
The salt was added at high conc.
[C ]
Conc. of the added salt is [CZ]
[C+][CZ]
 K [M  ]
 [P ]  the conc. of living and the conc. of free ion
[ CZ ]
   K [M  ]
[P (C )]  [M ]
[ CZ ]

Hence
(k p  k p )K
k papp  k p 
[ CZ ] k papp
originally
slope  (k p  k p )K
k p [P  ]  k  [P  ( C  )]
k papp  
int  k p
[M ]
[CZ ]
Then able to get k k , K from the two graphs.
-
p, p


Hanyang Univ.
 Spring 2008

Anionic Polymerization
Effect of gegen ion on Anionic Polymerization of Styrene
THF Dioxane
kp K107 kp- kp 

Li+ 160 2.2 6.5104 0.94

Na+ 80 1.5 3.4
K+ 60~80 0.8 19.8
Rb+ 50~80 0.1 21.5
C S+ 22 0.02 24.5

- Why kp- is the same value?

; kp- is much more larger than kp
Thus we can say that reactivity of free ion is much greater than that of ion pairs.

- In the case of dioxane?

;In dioxane which is tend not to be solvated, it has reverse tendency comparing to the case of THF.
Solvation is not important in dioxane.
Cs is too high and there is no difference.

Hanyang Univ.
 Spring 2008

Anionic Polymerization
Li+ genenion in aromatic hydrocarbon
R p  k p [M : Li  ][M]
R i  k i [RLi ][M] Look at difference.
Unassociated species
Let’s say we are using the BuLi initiator.
solvation as well as  is important!

Although, the 1,2 diethoxyethane reduce the , kp varies 1~1000 fold because of highly
solvating ether .

Reactivity of free ion < Reacitivity of ion pair

In aromatic hydrocarbon, unassociated species dominate rate.

Depends on the unassociated species in very low conc.
K1
(C4H9Li)6 6C4H9Li
K2
n - +
(R Mn-Li+)2 2C4H9 Mn Li
H H
Li
CH2 C CH CH2 2 CH2 CLi
Li
R R R
Covalent character

Hanyang Univ.
 Spring 2008

Anionic Polymerization
Evidence — the viscosity measurement before and after term, we find that living

polymer is associated after termination, viscosity drops.

1 1
[RLi ]  K 16 [( C 4 H 9 Li ) 6 ] 6

1
Ri  [ ]6
1 1
   
[M : Li ]  K 22 [(M : Li ) 2 ]2
1
order in the R 
2
1
order in initiation rate
6

Because initiators and ion pairs are reduced,

Polymerization reaction in Aliphatic HC is lower than inaromatic HC.

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 Spring 2008

Anionic Polymerization
Lenz P.437 Table 13-9

Effect of solvent and gengenion on Copolymerization of Styrene and isoprene at 25C

% Styrene in copolymer
Solvent Na+ counter ion Li+ counter ion

Nonsolvent 66 15
Benzene 66 15
Triethyl ether 77 59
Ethyl ether 75 68
THF(highly saturating 80 80
solvent)
Generally sodium is
more ionic than
lithium

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 Spring 2008

Cationic Polymerization
The growing chain bears a positive charge.
The active sites are either carbenium ions or oxonium ions.

Electron donating groups are needed as the R groups

because these can stabilize the propagating species by resonance.

Ex)

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 Spring 2008

Cationic Initiators
Proton acids with unreactive counterions

Lewis acid + other reactive compound:

* To use Lewis acid effectively as initiators, use the co-initiator.

.F.
F : .B. + C2H5Cl C2H5 + [BF3Cl]
F cationogen

Hanyang Univ.
 Spring 2008

Cationic Polymerization
Typical Initiator Systems
Co-initiator Initiator
SnCl4 H2O
AlCl3 HCl More acidic initiators are the most
H2SO4 H2SO4 effective in initiating polymerization

Order of reactivity AlCl3 > AlRCl2 > AlR2Cl >AlR3 

HCl > CH3COOH > C6H5NO2 > OH > H2O >> CH3OH > CH3COCH3
ke +
Ex) BF3 + H2O BF3OH H

C C
+   +
BF3OH H + C C H3C C B F3OH
C C

isobutylene
C
+   kp
H3C C C C C BF3O H + C C
C

Hanyang Univ.
 Spring 2008

Cationic Polymerization
Termination
C C C B F3OH C + HB-F3OH

C C
H
C

Problem : temination reactions occur randomly.

Kinetics
 
R i  k i M  H B F3 O H   k i K e M H 2 OBF3 
 
R p  k p M    BF3OH 
R i  R t S S Rt  kt   BF3OH   k i K e M H 2OBF3 
kiKe
   BF3OH   M H 2OBF3 
kt

[ * ] can control rxn

k pkiK e * *
Rp  H 2OBF3 M  2
kt
Hanyang Univ.
 Spring 2008

Cationic Polymerization
Rp kp M 
 Xn  
R t  R tr kt   k tr  M 

15
C 7
C C C
33

k tr 22

C C
1 3
C 6 B F3OH
17
C
21
+ 30 C C 32B F3OH
C C
16 C
27
C
34
8

k p M 
Xn 
k t  k tr M 

kt  0 X n  const. ,
ktr  0 X n  M 

Hanyang Univ.
 Spring 2008

Chain Transfer Reactions

-Cationic vinyl polymerization is plagued by numerous side reactions,
which lead to chain transfer mostly.

Ex)

• Difficult to achieve high MW

(*initiator can give rise to many separate
chains because of chain transfer)

• These side reactions can be minimized

But ! not eliminated by running the reaction
at low temperature

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 Spring 2008

Cationic Polymerization
1) Ring opening polymerization

(1) Mechanism

CH2 . . CH2 CH2

+ +
O R CH2 O + .O. ORCH2ORCH2 O
R R R
carbon type polymzn.

Example of ROR
: cyclic amides, sulfides, acetals, esters, lactam, alkanes, …

(2) Polymerizability

- unstable ring or the ring which cannot be cyclized easily are very reactive
* 3,4 and 7-11 membered ring is the most reactive ring
5,6 membered rings are stable and polymerize slowly,
but, it still possible to be polymerized.
**3-membered ring is the most easiest to be polymerized

Hanyang Univ.
 Spring 2008

Cationic Polymerization
(3) polymerization of THF(Polytetrahydrofuran)
2 PF5 PF4 + (PF6) -

+ -
PF4 + (PF6) - + O PF4 O PF6
gegenion
if H2O exist in the co-catalyst, the polymerization rate increases.
If the living polymerization is possible to occur, thus the termination or transfer also could be occurred.

+ (CH2)4
O (CH2)4 O +O (CH2)4
A-
+ (CH2)4
O(CH2)4O(CH2)4 O
-
A (CH2)4
O

O(CH2)4O(CH2)4 O(CH2)4
+
+
O- (CH2)4
A
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 Spring 2008

Cationic Polymerization
(4)Kinetics
Initiation
K + -
I + ZY Y (IZ)
initiator coinitiator
- ki -
YM+(IZ)
+
Y (IZ) + M
Ri  k i [Y ( IZ )  ][ M ]  Kk i [ I ][ ZY ][ M ]


ex) styrene, stannic-chloride-H2O System [SnCl4OH-]H+

Propagation – can has a low activation energy and can be polymerized rapidly
+
Mn O + O Mn O (CH2)4O  or

Simple propagation reaction

H
+ -
CH2 C [SnCl4OH] + H2C CH CH2CHCH2
R R R
strong initiator
R p  k p [ M  ][ M ]
The total rate of polymerization may actually increases by decreasing the temperature,
which means that the termination has a high activation energy.
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