Spring 2008

Chap 9. Chain-growth Polymerization

Chain-Growth Polymerization (Addition) Processes

1. Free radical Initiation Processes

2. Cationically Initiated Processes

3. Anionically Initiated Processes

4. Group Transfer Polymerization

5. Coordination Polymerization

Hanyang Univ.
 Spring 2008

Chain-Growth Polymerization
1. Only growth reaction adds repeating units one at a time to the chain

2. Monomer concentration decreases steadily throughout the reaction

3. High Molecular weight polymer is formed at once; polymer molecular

weight changes little throughout the reaction.

4. Long reaction times give high yields but affect molecular weight little.

5. Reaction mixture contains only monomer, high polymer, and about 10-8
part of growing chains.

Step-Growth Polymerization
1. Molecular weight increases steadily.

2. High molecular weight polymers are found at the end.

3. Long reaction time needs to synthesize high conversion and high molecular weight.

Hanyang Univ.
 Spring 2008

Chain Growth Polymerization

(1) Initiation
kd : Initiator decomposition rate constant
: 10-4 ~ 10-6 L/mole sec

Bond Energy = 46 kcal/mole

Heat (60ºC)
UV kd

AIBN Primary radical

Unstable radical

Ri  ki M I 
Hanyang Univ.
 Spring 2008

Chain Growth Polymerization

(2) Propagation (Repetition of similar reaction)

R p  k p M M 

kp : 102 ~ 104 L/mole sec (much faster than step-growth polymerization)

Hanyang Univ.
 Spring 2008

Chain Growth Polymerization

(3) Termination

(a) Coupling or combination

Hanyang Univ.
 Spring 2008

Chain Growth Polymerization

(3) Termination
(b) Disproportionation

ktd

ktd

kt=ktc+ktd 106 ~ 108 L/mole sec

Rt  kk M M   Rt M 
2

Hanyang Univ.
 Spring 2008

Chain Growth Polymerization

(4) Chain Transfer

Physical chain length

Monomer, Polymer, Solvent or Chain transfer agent

Kinetic chain length

Hanyang Univ.
 Spring 2008

Chain Growth Polymerization

Kinetic Chain Length :

kinetic chain length υ of a radical chain polymerization is defined as the
average number of monomer molecules consumed (polymerized) per
each radical, which initiates a polymer chain.
Radical
ex) Monomer # 4000 1,2,3,4
Disproportionation

υ =4,000/4 =1,000
Determined by steps 1, 2, 3. (Initiation, propagation, and termination)
(No chain transfer)

Physical Chain Length :

This condition contains Step 1, 2, 3, 4.

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Non-Polymerization Reaction

Peroxide induced Bromination of Toluene

1) Initiation
Two types of reaction
 R-O-O-R 2RO• (1)
 R-O• + Br2 ROBr + Br• (2)
 R-O• + ФCH3 ROH + ФCH2• (3)

Two radicals and two kinetic chains are formed by decomposition of

each ROOR molecules

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

2) Propagation
 Br• + ФCH3 HBr + ФCH2 (4)
 ФCH2• + Br2 ФCH2Br + Br • (5)

Two special features

 The number of active species is fixed.
 Same reactions are repeated during the kinetic chain reaction.

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

3) Termination
 2 Br• Br2
 2ФCH2• ФCH2 CH2Ф
 ФCH2• + Br • ФCH2Br + Br •

Net Effect of Kinetic Chain Reaction:

One ROOR molecule can cause formation of Br2, CH2CH2, CH2Br,HBr, ‥.

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Comparison between Chain Polymerization & Chain Reaction

Chain reaction Ri = Rt
Reaction Rate

Steady state

Time
Induction period
In proportion to the O2 concentration

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

In the case of Chain reaction, there are induction periods, due to the
existence of inhibitor.
When an active center is formed, the reaction rate would be faster and
then go to steady state.
The whole reaction rate is reaching a plateau region.
After that, reaction rate decreases due to a loss of monomers or initiators.

Linear Chain-Growth:
Polymer of high DPn found easily in early reaction

Linear Step-Growth:
high extent of reaction value required to obtain high DPn

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Comparison Free Radical Reaction & Ionic Reaction

- Ionic Initiation – multiple bond addition, ring opening polymerization

- Radical Initiation – Ring-opening polymerization is not initiated.

CH3 CH2 For the cationic initiation, it will not be free radical.
CH3
isobutylene

Ex) CH2 H2C

CH3
CH2
R + CH2 H + CH2
H3C
H3C
H3C Because of resonance stability

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Comparison between Free Radical Reaction & Ionic Reaction

Ionic Free Radical
Anionic Cationic
Ring opening + - -
End-groups Generally, combine with counter-ion or gegenion
E.g. R+ AlCl4―
Degree of association depends on below
Solvent-system polarity Truly Free Radical
Stability of end group (no association)
Type & size of scounter-ion
Temp.

Degree of association influences:

Reaction rates
Termination rate
Stereospecificity
Termination Depend on monomer unimolecular Combination or Bimolecular
consumption, Living polymer or disproportionation reaction combination or
Block copolymer disproportionation

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Comparison between Free Radical Reaction & Termination Step of Ionic Reaction

A) Free Radical Termination

.CH .CH CH ..
H
. .CH
CH2 CH CH
2
CH2
X X X X

ktc (coupling ktd (disproportionation)

or combination)

H
CH2 CH CH CH2
X X
CH CH + CH CH2
X X

Two molecules involved unsaturated group.

= bimolecular reaction

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

B) Cationic Termination

+
-
CH2 CH [XY]
R -
EX) AlCl4 ÀÌ °æ¿ì
-
X= Cl Y= AlCl3
X
CH2 CH + Y
R

Anionic capture is similar to combination of free radical reaction.

But, this reaction can’t include increasing of MW because of unimolecular reaction

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

..H
+ -
CH + [XY] + HY + Y
proton release R
R
The proton release is similar to disproportination of free radical..
But, one chain joins in the reaction unimolecular reaction

C) Anionic
C) Anionic Termination
Termination
Termination is rare but can occur by loss of a hydride ion
- +
CH 2 CH M
R
-
-H

CH CH + HM
R

Unimolecular type termination occurs

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Anionic Cationic Free Radical

Termination Termination Termination
Reaction rate Unimolecular Bimolecular
High concentration of growing Relativity low
chains 10-2~10-3molar Rates 104~105 concentration 10-8~10-9
times higher than free radical molar occurs at high
Rates
E Activation Energies Similar
Chain Transfer Negligible + +
Disadvantage Rigorous Purity or precautions
Polymer System Solution or Bulk Wide variety of
polymer systems,
Gas, Solid, Solution,
Bulk, Precipitation,
Suspension, Emulsion

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Free Radical Initiated Polymerization of Unsaturated monomers

Kinetic Scheme

Initiation
Two step sequence-Both enter into overall rate
1. Initiator decomposition
kd
I2 2I

2. Addition of Initiator fragment to the monomer, Initiation of Chain growth.

ki
I+M IM
Primary radical species
The efficiency of Initiator - Determined by competition of desired reaction and side reaction

Generally, 0.5 << f << 1

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

A.Cage Effect –primary recombination

Initiator fragments surrounded by restricting cage of solvent

Ex) O O
C H3 C O O C C H3

O O
H3C CH3
O O

(acetyl peroxide)

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

I) Recombination possible I2 2I

II) If elimination reaction occurs while the free radical in-cage,

Formation of stable molecules due to Radical combination.

And formation of Inactive Species.

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

B. Induced Decomposition –Secondary combination

I) Through Radical attack on peroxide molecules

R + R-O-O-R RH + ROOR R=O + RO

Finally, R + ROOR ROR+ RO

Total number of radical does not change, but among them half molecules were wasted.

II) Chain Transfer to Solvent

(In this case, since just one radical was obtained half molecules were wasted.)

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

III) Reaction with Chain Radical

I. + M IMn .

IMn . + I2 IMnI + I.

Since not all Molecules participate in the initiation → Efficiency factor

f: Initiator Efficiency
= mole fraction of initiator fragments that actually initiate polymer chains.
0.5 < f < 1.0

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

C. Reaction Rate
d [ M ]
Ri 
dt
 ki [ I ][ M ]
by convention, two radical formation.

 2 fk d [ I 2 ]
If [M] is representative for the concentration of chain radical,

That is , M = IM
or = I [M]

f  1 Ri is unrelated with [M]

f=[M]
f < 1 Ri is related with [M]

[M] , f
[I2] , f due to induced decomposition
Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

D. Initiator
O O S S N N - containing compounds.

O O
CH3 C O O C CH3 Acetyl peroxide 80~100C

O O
C O O C Benzoyl peroxide 80~100C

CH3 CH3
C O O C Cumyl peroxide 120~140C
CH3 CH3

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

CH3 CH3
H3C O O CH3 t-butyl peroxide
CH3 CH3

CH3
H3C O OH Hydroperoxides, cumyl or t-butyl
80~100C
CH3

CH3 CH3
CH3
CH3 C N N C CH3 2 CH3 C . + N2
50~70C
CN CN CN

AIBN 2,2 azobisisobutyronitrile

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Propagation
d[M ]
Rp    k p [ M ][ M ]
dt
kp
I   M  IM 2 
kp
             IM n 
Termination
M. .M

ktc ktd
d [ M ]
Rt    2( ktc  ktd )[ M ]2
dt
By convention
Since 2 radical elimination
Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Overall Rate of Polymerzation

R o  k i [I][M]  k p [M][M]
(# of propagation step >>> # of initiation step)

R o ~ R p  k p [M][M]

Radical concentration

• Difficulty of measurement, low concentration. (~10-8molar)

• Thus, it is impractical using this therm.

• [M] elimination is desirable.

Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

[M] elimination methods
Steady-State Assumption

Radical concentration increases at the start, comes to steady state simultaneously

and then reaction rate change becomes 0. (active centers created and destroyed at the same time)
Ri = Rt

2 fk d [ I 2 ]  2(ktc  ktd )[M ]2

1 1
fk d
[ M ]  ( ) 2 [ I 2 ]2
ktc  ktd
1
R
or  [ i ]2
2 Rt
d[M ]
R    k  [ M ][M ]
dt
1 1
fk
 k  [ M ][ I 2]2 ( d
)2
ktc  ktd
Hanyang Univ.
 Spring 2008

Kinetic Chain Reaction

Mostly in case of f<1 system → [I2]1/2 (Square Root Dependence of [I2])

※ Odian Fig. 3-4 MMA using BPO

Rp
Vinyl Acetate
using AIBN

[I2]1/2
H
C O O C 2 C O -CO2 .
O O O
300C
BPO
CN CN CN

CH3 C N N C CH3 2 CH3 C. + N2

CH3 CH3 CH3

Azobisisobutyronitrile Hanyang Univ.

 Spring 2008

Kinetic Chain Reaction

1
+ BPO +
system Rp  [ I 2 ] [M ]
2

In case f < 1, but SRD is not applicable,

1 3
+ BPO + CH3
Rp  [ I 2 ] [M ]
2 2

Because f is ‘dependent’ on [M]

Why?

Due to induced decomposition of toluene + [I2]

Hanyang Univ.
 Spring 2008

Kinetic Chain Length (KCL)

At S-S assumption
(1) Disproportionation
the average number of monomer molecules consumed (polymeriz ed)
KCL 
each radical (initiates a polymer chain)
Rp

Rt ( Ri )
Knowing that
d[M]
R t  R td  R tc 
dt
(2) Coupling or combination

1
the rate const.  k tc ( 1 polymer product from 2 polymer chains)
2
d [ M ]
Rtc  
dt term
Hanyang Univ.
 Spring 2008

Kinetic Chain Length (KCL)

(3) Both (1)+(2)

Rp Rp 2R p 2R p
KCL    
Rt R  1 R R td  R tc  R td R td
td tc R t (1  )
2 Rt

Rtd
define y  : fraction of termination caused by disproport ionation
Rt
2R p
in this case, KCL 
Rt (1  y )

Hanyang Univ.
 Spring 2008

Kinetic Chain Length (KCL)

Degree of Polymerization
The more concentration of monomer, DPn
The less concentration of initiator, DPn

Monomer consumption rate  d [ M ] / dt

DPn  
polymer formation rate d [ Polymer ] / dt

(1) Dispropotionation

DPn  

(2) Coupling

DPn  2
Hanyang Univ.
 Spring 2008

Kinetic Chain Length (KCL)

(3) Dispropotionation & Coupling
1
Polymer 생성속도
Polymer formation rate  R td  R tc
2
모노머 consumption
Monomer 소비속도 rate  R p

Rp 2R p R td
DPn    (1) where y
R td
1
 R tc R t (1  y ) Rt
2
2
DPn 
1 y
1
k 2
knowing that R p  k p  d f[I 2 ] [M]  ( 2)
kt 
R t  R i  2fk d [I 2 ]  (3)

Hanyang Univ.
 Spring 2008

Kinetic Chain Length (KCL)

From (1),(2),(3)
In case of no Chain transfer, and valid S-S assumption

k p [M ]
DPn  1
 (4)
 kd  2
(1  y )kt  f [ I 2 ]
 kt 

k p 2 [M]2
or DPn  (5)
(1  y)k t R p

Hanyang Univ.
 Spring 2008

Chain Transfer
M + XY MX + Y
Chain transfer agent

If Chain transfer occurs Rp is unchangable but has an effect on DPn

(∵ Since [Y] instead of Rp=kp[M][M] )

ex)

H H H H

R C C. + C C Cl
.
C lC 4 R + CCl3

H X H X

(1) Chain transfer occurs by solvents or additives

In this case, High chain transfer coefficient.

(2) Transfer occurs by monomer or polymer

Hanyang Univ.
 Spring 2008

Chain Transfer
Inhibitor and Retarder
 Inhibitor
When Y take part in chain opening reaction, polymer moves from one site to another.
In this case, hydroquinone etc. are used as inhibitor.

 Retarder
When the reactivity of Y is low, controlling the MW of the monomer including
these two materials, Mercaptan etc. are used as Retarder.

Like this, when chain transfer condition arises

d [ Polymer ] 1
 Rtd  Rtc   Rtr
dt 2
Rp 2Rp
 DPn  
d [ Polymer ] Rt (1  y )  2 Rtr
dt
2k p [ M ][ M ]

2k t [ M ]2 (1  y )  2 k tr [ M ][ XY ]
k p [M ]

k t [ M ](1  y )   k tr [ XY ]
1
kd f
Knowing that [ M ]  { [ I 2 ]} 2
kt
Hanyang Univ.
 Spring 2008

Chain Transfer
k p [M ]
DPn  1
k  2
k t (1  y )  d f  [ I 2 ]   k tr [ XY ]
 kt 
1
1 k (1  y )  k d
 t  


 2k tr [ XY ]
f [ I 2 
]
DPn k p [ M ]  kt  k p [M ]
1 1 k [S ] k [T ]
  tr , s  tr ,t  
DPn DPn , 0 k p [M ] k p [M ]
1 1 [S ] [T ]
  CS  CT  
DPn DPn , 0 [M ] [M ]

1
See Odian
DPn P.235
From the slope of a graph
Chain transfer coefficient ‘Cs’

[5]/[M]
Hanyang Univ.
 Spring 2008

Temperature Dependence of Rp and DPn

Assume : no chain transfer
1

 k d  2
R p  k p  f  [I 2 ]
 [M]

 k t
  

 1 1
  k d 2
   ln[ f[I 2 ]] 2  (1)
ln R p  ln[M]  ln k p  
k
  t  
 
E  / RT
k p  k p e Ep 5 ~ 8 kcal / mole
k d  k  d e E d / RT Ed 30 kcal / mole
k t  k  t e E t / RT Et 2 ~ 5 kcal / mole

Hanyang Univ.
 Spring 2008

Temperature Dependence of Rp and DPn

From Eq(1), and assume [I 2 ], [M]  const, f independent of T.

1
 kd
2
d ln[k p   ]
d ln R p  kt 

dT dT
E E
Ep  t  d
 2 2  7  2  15  0
RT 2 RT 2

 slope of lnRp/T is ( + )

 as T  lnRp 

but Rate of Increase  as d lnRp/dT 

Hanyang Univ.
 Spring 2008

Temperature Dependence of Rp and DPn

2R p Rp Rp
DPn  ,  
R t (1  y) Rt Ri

E t Ed
Ep  
d ln  2 2  7  2  15  0

dT RT 2 RT 2

 as T , ln   DPn 

[I]  Rp  but DPn 

T  DPn 

Hanyang Univ.
 Spring 2008

Ceiling Temperature Polymer-Depolymerization Equilibria

ㆍCeiling Temperature
Polymerization and Depolymerization are in equilibrium

ΔGp = ΔHp – TΔSp

ΔHp : Heat of polymerization
ΔSp : Molecular arrangement changes between monomer and polymer

At eq. State ΔGp=0

Monomers can no longer be persuaded to form polymers by chain

polymerization above a certain temperature. ceiling Temperature(Tc)

Hanyang Univ.
 Spring 2008

Rate Eq. of Polymerization Reactions

at Depolymerization prominent Temperature

If,

M Tc

Hanyang Univ.
 Spring 2008

Ceiling Temperature Polymer-Depolymerization Equilibria

k
kdp
sec-1

kp[M]

kp[M]- kdp

Tc
: No reaction above Tc
300 400 500 Tc Stable blow Tc

Hanyang Univ.
 Spring 2008

Ceiling Temperature Polymer-Depolymerization Equilibria

※Odian Fig 3-18

Monomer -H kcal/g mole TcC (bulk)
St 16 235
MMA 13 164
Ethylene 26 407
Propylene 21 300
-methyl St. 7 6

Entropy changes for all polymers are not so different.

Sp= Sp- Sm (–) value of Sp is higher

Hp= Hp- Hm if (–) , exothermic.

Hanyang Univ.
 Spring 2008

Trommsdorff Effect or Gel Effect

The increasing viscosity limits the rate of termination because of

diffusional limitations
restricted mobility of polymer radical

kp ( relative to [M] )

( ∵ kp const. in reaction progress, kt drop off in reaction progress )

→ Autoaccerelation effect

Hanyang Univ.
 Spring 2008

Trommsdorff Effect or Gel Effect

  1  e kt  one would expect ξ  as t  But ξ  as [[M0] 

80%

 60%

40%

10%
autoacceleratioan
as [M0] drastic in .

Hanyang Univ.