Chapter 6.

Free Radical Polymerization

6.1 Introduction
6.2 Free Radical Initiators.
6.3 Techniques of Free Radical Polymerization.
6.4 Kinetic and Mechanism of polymerization.
6.5 Stereochemistry of polymerization.
6.6 Polymerization of Dienes
6.7 Monomer Reactivity
6.8 Copolymerization.
 6. 1 Introduction
Type of polymerization.
Polymer: poly  many mer  many parts
(Greek) “Macromolecules”
Monomer: mono  single mer  single part
Polymerization
polymerization
Monomer Polymer

Monomer Polymer

H2C CH2 addition CH2CH2

H2C CHCl addition

CH2CH
Cl
O ring-opening
H2C CH2 CH2CH2O

condensation
HOCH2CH2OH CH2CH2O
-H2O

O
condensation
HO CO2H O C
-H2O
 6. 1 Introduction
Type of polymerization.
Classified by polymerization mechanism:
(1) step-reaction or step-growth polymerization
(2) chain-reaction or chain-growth polymerization
(3) ring-opening polymerization (step- or chain-growth)
 N =N0(1-
 6. 1 Introduction p
N0  N
N0 p)
Type of polymerization.
N0 1
Carothers DP  
p : conversion ratio N0 : initial number of molecules N (1  p)
N : the total number of molecules at a given time
1
at 98% conversion: DP   50
1  0.98
Table 1.1. Comparison of Step-Reaction and Chain-Reaction Polymerization
Step Reaction Chain Reaction

Growth occurs throughout matrix by Growth occurs by successive addition of

reaction between monomers, oligomers, monomer units to limited number of
and polymers growing chains

DPa low to moderate DP can be very high

Monomer consumed rapidly while Monomer consumed relatively slowly, but

molecular weight increases slowly molecular weight increases rapidly

No initiator needed; same reaction Initiation and propagation mechanisms

mechanism throughout different

No termination step; end groups still reactive Usually chain-terminating step involved

Polymerization rate decreases steadily as Polymerization rate increase initially as

functional groups consumed initiator units generated; remains relatively
constant until monomer depleted

a
DP, average degree of polymerization.
  6. 1 Introduction

A. Type of polymerization.

polymerization

Addition polymerization Condensation polymerization

1. Free-radical polymerization

2. Ionic polymerization

3. Complex coordination polymerization

• The formation of polyvinyl monomer.

• CH2 = CHX
  6. 1 Introduction
Free-radical polymerization

• Free radical are independently-existing species that have unpaired electron.

Normally they are highly reactive with short life time.
• Free radical polymerization’s are chain polymerization’s in which each polymer
molecules grows by addition of monomer to a terminal free-radical reactive site
known as active center.
• After each addition the free radical is transferred to the chain end.

• Chain polymerization is characterized by three distinct stages, Initiation,

propagation and termination.
B. Commercialized free-radical polymerization.
 1. peroxide and hydroperoxide
6.2 Free Radical Initiators. 2. azo compounds
3. redox initiator
4. photoinitiator
 6.2.1 Peroxides and Hydroperoxides

A. Benzoyl peroxide and other peroxides

 
a. Thermal decomposition of BPO.
 

b. Half-life of benzoyloxy radical : 30 min at 100℃

c. Cage effect : confining effect of solvent molecules.

  6.2.1 Peroxides and Hydroperoxides

O O

Ph C O O C Ph + Ph ·
(6.5)
O Ph O O O

Ph C O O C Ph Ph C O ·
Ph + HO C Ph
·
d. Other peroxides.

Diacetyl peroxide        Di-t-butyl peroxide

  Diacetyl peroxide      Di-t-butyl peroxide
                          (half-life:10hours at 120℃)
  6.2.1 Peroxides and Hydroperoxides

e. Promoters : Inducing initiation at lower temperature.

O O
Ph C O O C Ph + Ph N(CH3)2
(6.9)
CH3 O
Ph +N O C Ph + Ph CO2-
CH3

CH3 O
O
Ph +
N O C Ph + (6.10)
Ph N(CH3)2 + Ph C O
CH3
 6.2.1 Peroxides and Hydroperoxides

B. Hydroperoxide
 
a. Thermal decomposition hydroperoxide

 b. Cumyl hydroperoxide.

OOH
Ph C(CH3)2
 6.2.2 Azo Compounds.

  

A. α,α'-Azobis(isobutyronitrile) (AIBN).
 
a. Decomposition of AIBN.

b. Half-life of isobutyronitrile radical : 1.3 hours at 80℃.

 6.2.2 Azo Compounds.

B. Side reaction : Cage effect.

 
a. Tetramethylsuccinonitrile

b. Ketenimine                
 6.2.3 Redox Initiators.

  A. One electron transfer reaction.

 
a. Making free radical by one electron transfer
by redox reaction.
  b. Low-temperature reaction.
 c. Emulsion polymerization.
                                                                                                                    
   B. Example of redox system.
 6.2.4 Photoinitiator

A. Peroxide and Azo compound.

 
Photolysis and thermalysis.

B. Photolabile initiator.
 6.2.5 Thermal Polymerization.

A. Polymerization without initiators.

 
a. Dimer formation by Diels-Alder reaction.

The Diels-Alder reaction is an

organic chemical reaction (specifically, a cycloaddition)
2CH2 CHPh between a conjugated diene and a substituted alkene,
commonly termed the dienophile, to form a substituted
cyclohexene system.
H Otto Paul Hermann Diels and Kurt Alder first
Ph documented the novel reaction in 1928 for which they
were awarded the Nobel Prize in Chemistry in 1950 for
10 their work on the eponymous reaction.

b. Radical formation from dimer.

·
10 + CH2 CHPh ·
CH3CHPh +

Ph
11 12
 6.2.6 Electrochemical Polymerization.

A. Polymerization of electrolysis.

  a. Cathode reaction :
electron transfer to monomer molecule to form radical anion (6.22)

b. Anode reaction :
electron transfer to anode to form radical cation (6.23) 

B. useful for Coating metal surfaces with polymer films.

 6.3 Techniques of Free Radical Polymerization.
  6.3 Techniques of Free Radical Polymerization.

 6.3.2 bulk .
● Neat monomer (and initiator)
● Simplest formulation and equipment
● Most difficult in control, when polymerization is very exothermic
● Common problems: (1) heat transfer (2) increase in viscosity

● If polymer is insoluble in monomer  polymer precipitate

(1) viscosity would remain similar
(2) occlusion of radicals (within the polymer droplet) is unavoidable

● Radical occlusion  autoacceleration  crosslinked polymer nodules

(i.e. popcorn polymerization)

● The crosslinked nodules (light weight and large volume) may cause
fouling or fracture of the polymerization apparatus
Commercial uses
1. Casting formulations
2. Low MW polymers for adhesives, plasticizers, tackifiers,
and lubricant additives
  6.3.2 Suspension.
Suspension polymerization

● Disperse monomer droplets in a noncompatible liquid (e.g. H2O)

● Polymerize the monomer by an initiator (soluble in the monomer)
● Stabilize the dispersion with a stabilizer (e.g. poly(vinyl alcohol) or
methyl cellulose)
● Isolate granular bead products by filtration or spray drying

● Heat transfer is efficient and reaction is easily controlled

● Similar to bulk polymerization in kinetics and mechanism
● Not applicable for tacky polymers (e.g. elastomers)
due to the tendency of agglomeration

Commercial uses
For making granular polymers, e.g. PS, PVC, PMMA
 6.3.3 Solution.

● Use monomer solution

● Heat transfer is very efficient
● MW may be severely limited by chain transfer reaction
(probably caused by the solvent molecule or its impurities)

● Solvent residues  difficult to remove completely

● Environmental concerns  organic solvent waste

Use supercritical CO2 as a polymerization solvent 

nontoxic, inexpensive, easily removed and recycled
  6.3.4 Emulsion.
● Developed in 1920s at Goodyear Tire and Rubber Co.
● Widely used for large-scale preparation
● For water-based (latex) paints or adhesives

Emulsion  oil-in-water. Inverse emulsion  water-in-oil (less stable)

  6.3.4 Emulsion.
Emulsification
•Add emulsifying agent (e.g., soap or detergent) in an aqueous solution
 to form micelles
• Monomers enter and swell the micelles
Initiation
● Radicals (redox type) are generated in the aqueous phase and diffuse into micelles
Propagation
● Polymerization propagated within micelles
● More monomers enter micelles to support the polymerization
Termination
● Termination by radical combination when a new radical enters the
micelle

Results
● Extremely high MW are obtainable, but often too high to be useful
● Chain transfer reagents are often added to control the MW
● Also suitable for tacky polymers (∵ small particles are relative stable and can resist
agglomeration)
  6.3.4 Emulsion.
TABLE 6.3. Typical Emulsion Polymerization Recipesa
Styrene-Buradiene Polyacrylate
Ingredients, Conditions
Copolymer Latex
Ingredients (parts by weight)
Water 190 133
Butadiene 70 -
Styrene 30 -
Ethyl acrylate - 93
2-Chloroethyl vinyl ether - 5
p-Divinylbenzene - 2
Soap 5 3b
Potassium persulfate 0.3 1
1-Dodecanethiol 0.5 -
Sodium pyrophosphate - 0.7

Conditions
Time 12hr 8hr
Temperature 50oC 60oC
Yield 65% 100%
a
Recipes from Cooper.23
b
Sodium lauryl sulfate.
6.4 Kinetic and Mechanism of polymerization.

A. Mechanism of free-radical polymerization.

 
a. Initiation.
  
1) Decomposition.
     Initiator .→ 2R
  
2) Addition.

(6.25)
6.4 Kinetic and Mechanism of polymerization.
b. Propagation.

(6.26)

 1) Head-to-tail orientation : predominant reaction.

      Steric and electronic effects.
  
2) Examples of not exclusively head-to-tail orientation.

(13-17% of head to head)   (5-6% of head to head)   (19% of head to head)

6.4 Kinetic and Mechanism of polymerization.
 c. Termination.
(Combination, disproportionation, primary raidical termination )
 
 1) Combination.

(6.27)

Polystyrene radical (combination (77 %) + disproportionation (23 %)).

(6.29)
 6.4 Kinetic and Mechanism of polymerization.
 2) Disproportionation (79 %).
(6.28)

Poly(methyl methacrylate) radical.

CH3 CH3 CH3

2 CH2C CH2CH + CH=C

CO2CH3 CO2CH3 CO2CH3

(6.30)
CH2

or CH2 C

CO2CH3

3) Promary Radical Temination

● combines with initiator radicals
 at high initiator levels under very high viscosity

(6.31)
 6.4 Kinetic and Mechanism of polymerization.
- Acrylonitrile : Combination virtually exclusively at 60℃.

- Poly(vinyl acetate) : Disproportionation (100 %).

 Factors favor disproportionation 

Steric repulsion
Availability of -H for H-transfer
Electrostatic repulsion induced by the polar group (e.g., ester)

 polyacrylonitrile  stable R• → chain coupling

 poly(vinyl acetate)  unstable R• → chain disproportionation

H H
CH2 C C N (resonance stabilization) CH2 C OAc (unstable)
 
B. Kinetic of free radical polymerization.

Initiation
kd
Initiator R
ki
R +M M1
Propagation
kp
M1 + M M2
kp
M2 + M M3
kp
Mx + M M(x+1)
Termination
ktc Coupling
Mx + My M(x+y)
ktd
Mx + My Mx + My Disproportionation
 B. Kinetic of free radical polymerization.
 
a. Assumption.
 
1) The rates of initiation, propagation, and termination are all different.
  2) Independent of chain length. (but 동일한 속도로 진행 )
  3) Negligible end group.
  4) At steady state, constant radical concentration (- d[M.]/dt = 0).
    (steady state assumption)

 b. Initiation (Ri)

              
-d[M ·]
Ri = = 2fkd[I]
dt
f : Initiator efficiency. f : initiator efficiency (0.3-0.8)
            radicals that initiate a polymer chain
f=
radicals formed from initiator

kd : Decomposition rate constant.

  [I] : molar concentration of initiator.
 [M ·] : molar concentration of radical.
 B. Kinetic of free radical polymerization.
 c. Termination rate ( Rt )
      -d[M ·]
Rt = = 2kt[M ·]2
         dt
kt = ktc+ ktd

 d. Propagation rate ( Rp )

    
   Steady state assumption.
Ri=Rt
Formation and destruction of radicals occur at the same rates
(assuming the majority of polymers are formed during the steady state)
[M·] remains constant  Ri = Rt

-d[M]
Rp = = kp[M][M ·]
2 fkd[ I ]  2kt[ M ] 2 dt

fkd[ I ] -d[M] fkd[ I ]

[M ·]= = kp[M]
kt Rp =
dt kt
B. Kinetic of free radical polymerization.

e. Average kinetic chain length ( ) 

(Rt = Ri at steady state)

 Disproportionation : DP = 
   
Combination : DP = 2
B. Kinetic of free radical polymerization (Deviation).

Kinetics deviate from normal conditions

1. As viscosity becomes very high 
(bulk or concentrated solution polymerization)
2. when polymer precipitates
3. when chain transfer reaction occurs

Kinetics deviation in bulk or concentrated solution polymerization

● As viscosity become very high

 Chain mobility reduce
 Termination rate decrease (higher MW)
 Polymerization rate autoaccelerate
 Reaction exotherm increase
 Gel forms

● Gel effect / Trommsdorff effect / Norris-smith effect

B. Kinetic of free radical polymerization (Deviation).

 f. Gel effect : Trommsdorff effect, Norris-smith effect.

  
1) Difficult termination reaction because of viscosity.
  
2) Ease propagation reaction because monomer size is small,
     even though high viscosity.
  
3) Autoacceleration by exotherm of propagation reaction.
  
4) To obtain extraordinary high molecular weight polymer like gel.
B. Kinetic of free radical polymerization (Deviation).

Kinetics deviate from normal conditions

1. As viscosity becomes very high 
(bulk or concentrated solution polymerization)
2. when polymer precipitates
3. when chain transfer reaction occurs

Chain transfer —
terminate the growing chain by generating a new radical species
low MW / broad MWD / chain branching
 C. Chain transfer reactions :
Growing radicals move to other parts

   by hydrogen abstracting.

   Lowering average kinetic chain length.
 
* Growing radicals move to other polymer chain.
CH + CH2CH CH2 + CH2C

Y Y Y Y
(6.32)
( CH2CHY highly branched (mostly contain 3
CH2C
CH2 CHY or 4 C in length)
Y

* Backbiting self polymer chain.

branched (mostly contain 5 or 6

(6.33) membered cyclic transition states)

 LDPE : branching polymer.

 C. Chain transfer reactions

 a. Moving to initiators or monomers.

(6.34)

(6.35)

Chain transfer to monomer (6.38)  in the presence of allylic H

● Polypropylene cannot be prepared by free radical polymerization

CH3 CH3
CH2CH  + CH3CH CH2 CH2CH2 + CH2 CH CH2  (6.38)
 C. Chain transfer reactions
Methyl methacrylate

Competition reactions:
(A) Chain transfer to monomer  allylic radical
(B) Chain addition to monomer  3 and resonance-stabilized radical

CH3 CH2 CH3 CH3 CH3 CH3

A B
CH2 C H CH2 C CH2 C CH2 C
CO2Me CO2Me CO2Me CO2Me CO2Me C
O OMe

 Chain addition is favored (because B create a more stable radical)

 PMMA can be prepared via radial polymerization

 b. Moving to solvent.

Polystyrene made in CCl4 contains Cl due to Cl transfer (6.36)(6.37)

(6.36)

(6.37)
 C. Chain transfer reactions (cf. 182 p)

c. Moving to chain transfer agent.

(6.39)

1 1  C [T ]
t
= +
tr  [M ]
         
  Ct : Chain transfer constant.
   [T] : Concentration of chain transfer agent.

 
d. Telomerization : At high concentration of transfer agent,
ktr>kp.
    Low-molecular-weight polymers are obtained.
              (Telomer)
Alkylated phenol

● Very good stabilizer for monomer

● Inhibit free radical polymerization via chain transfer reactions
● Facilitate monomer shipment and storage

When monomers contain inhibitors

● Remove inhibitors (by distillation or extraction)
● Add extra initiator (to consume the inhibitor)
● Exclude O2 (which is also a radical inhibitor)
● Usually exhibit an induction period
 D. Living free radical polymerization :
Atom transfer polymerization.

Living polymerization / living polymers

● Absence of chain termination or chain transfer
● Chain ends remain active all the time
● Add more monomer  increase MW
● Add different monomer  form block copolymer
● First reported for an anionic polymerization system (1950s)
● Low polydispersity (as low as 1.05)

Living polymerization by atom transfer polymerization

(for radical polymerization)
 D. Living free radical polymerization :
Atom transfer polymerization.

  a. Copper(I) bypyridyl(bpy) complex: 

● Polymerization of styrene
with 1-chloro-1-phenylethane and Cu(I)(bpy) complex

*Bipyridyl =
N N
 D. Living free radical polymerization :
Atom transfer polymerization.
 b. TEMPO (18) : 2,2,6,6-tetramethylpiperidinyl-1-oxy.
● Polymerize styrene with benzoyl peroxide plus TEMPO
(2,2,6,6-tetramethylpiperidinyl-1-oxy)

● TEMPO is too stable to initiate the polymerization

● TEMPO can promote the decomposition of peroxide,
forming the initial radical
● TEMPO combines reversibly with chain ends,
keeping them alive (6.45)

TEMPO
 6.5 Stereochemistry of polymerization.
A. General consideration.
 
a. Stereoregular polymerization :
Ionic and complex coordination polymerization.

   1) Terminal ion pair : counter ion.

   2) Terminal complex active site.
   3) Low temperature.

 b. Stereo-irregular polymerization :

Free-radical polymerization.

   1) No stereoregulating radical terminal group.

   2) Somewhat higher temperature.

Consideration factors:
(1) interaction between chain end and monomer
(2) influence by the configuration of penultimate repeating unit
끝에서 2 번째에 있는
 6.5 Stereochemistry of polymerization.
Approach of monomer

If rotation does not occur before monomer addition:

(1) mirror approach (6.46)  isotactic

(2) nonmirror approach (6.47)  syndiotactic

mirror approach isotactic

nonmirror approach syndiotactic

 6.5 Stereochemistry of polymerization.
● Radical polymerization usually lack of stereoregularity, because:
(1) radical center is sp2 (less crowded)
(2) no counter ions

Syndiotactic PMMA

● By radical polymerization below 0℃

● First reported in 1958
● Possible due to steric influence of penultimate unit (6.48)
(1) if the radical center assumes substantially a sp3 hybridization
(2) assumes rotation is slower than propagation
 6.5 Stereochemistry of polymerization.
"
sp3" CO2Me
H C C
CH3
H
H C H CH3
C CH3 H C CO2Me
CO2Me C
H "sp2"
C CO Me
P CH
2 C
3 P CO2Me
CH3
influence of the penultimate unit
monomer and terminal unit interaction

● If the radical center assumes a sp2 planar structure (6.47), then

(1) the interaction between monomer and chain end would dominate,
(2) and adapt a nonmirror arrangement
6.6 Polymerization of Dienes

  6.6.1 Isolated Dienes

A. Crosslinked or cyclopolymerization.
 6.6 Polymerization of Dienes
Diallyl monomers
● for making highly cross-linked thermosetting allyl resins
(or as a crosslinking agent)

● Uses of monomer 21 
(1) For electrical or electronic items
(circuit boards, insulators, television components, etc.)
(2) For fiber-reinforced plastics
(for pre-impregnating glass cloth or fiber)
● Uses of monomer 22 
(1) For applications requiring good optical clarity
(2) eyeware lenses, camera filter, panel covers
 6.6.2 Conjugated Dienes.
● Can undergoes 1,2- and /or 1,4-addition

1,2- cis-1,4 trans-1,4

Radical polymerization of 1,3-butadiene

• 1,2-addition (20%) ; 1,4-addition (80%) with majorly trans
• increase T
 increase cis-1,4 structure
 but keep the same 1,2-/1,4- ratio (Table 6.6)
6.6.2 Conjugated Dienes.
6.7 Monomer Reactivity

A. Thermodynamic feasibility.
 
a. ΔGp = ΔHp - TΔSp
     ΔGp : Gibbs free energy change of polymerization.
     ΔHp : Enthalpy change of polymerization.
     ΔSp : Entropy change of polymerization.
     ΔGp < 0 : favorable free energy of polymerization.
 
b. Values of ΔH and ΔS for several monomers.
 
c. Polypropylene and isobutylene :
   
  ΔG < 0 → unfavorable polymerization.
     because of kinetic feasibility
 6.7 Monomer Reactivity
TABLE 6.7. Representative Enthalpies, H, and
Entropies, S, of Polymerizationa
-H -S ΔGp = ΔHp - TΔSp
Monomer (kJ/mol) (J/mol)

Acrylonitrileb 77 109 However, propylene or isobutylene

78 89 (contain allylic H)
1,3-Butadiene
109 155
Ethylene CH3
Isoprene 75 101
65
CH3 CH CH2 , CH3 C CH2
Methyl methacrylate 117
Propylene 84 116
70 ● dose not undergo normal free
Styrene 104
radical polymerization
Tetrafluoroethylene 163 - ● due to the propensity for chain
Vinyl acetate 90 - transfer of the allylic H
Vinyl chloride 71 -
a
Values selected from Ivin.29c Polymerization temperature
25oC unless otherwise indicated.
b
74.5oC.
c
127oC.
 6.7 Monomer Reactivity

Reactivity of monomers 
(1) Stability of monomer
(2) Stability of monomer radical
(more important)

Styrene
• Its vinyl group should be stable
due to conjugation resonance with the phenyl ring
• Polymerization however still undergoes readily
 due to the formation of highly stable radical (33)
 6.7 Monomer Reactivity
(1) In gas phase, addition to ethyl radicals 
acrylonitrile ＞ styrene ＞ vinyl acetate  radical stabilization effect

C N  OAc
(2) In solution phase, polar effect make acrylonitrile very stable

(3) Incorporation of 14C into polymer (in solution)

(or monomer reactivity toward benzoyloxy radical)
styrene ＞ vinyl acetate ＞ acrylonitrile

O O
Ph C O O C Ph Ph14CO2
14 14 
Ph14CO2 Ph 14
CO2 (6.52)

Ph14CO2 M Ph14CO2M (6.53)

 6.7 Monomer Reactivity
Monomer stability aspect (ref. Table 6.4)
● Vinyl acetate  very stable monomer
 but, high kp (2640)

● Styrene  unstable monomer

 but, low kp (176) (due to resonance stabilization)

● Acrylonitrile  although propagating radical is stabilized by –CN

 yet, high kp (1960)

● Methyl methacrylate has much smaller kp (515) than methyl

acrylate (2090)
 due to steric hindrance and the hyperconjugation stabilization
effect of the intermediate radicals
 6.7 Monomer Reactivity
Steric effects H2C=CHR, H2C=CR2, CHR=CHR

● 1,2-disubstituted monomers are most difficult to polymerize

(except F-containing monomers)

R R R R
C C C C
H H H H

F F F F
C C C C
H H
H H
● But, 1,2-disubstituted polymers are thermodynamically more stable
than 1,1-disubstituted polymers

R R H R
Stability: C C > C C  (∴ kinetic control)
n n
H H H R
 6.7 Monomer Reactivity
kp
Mx +M M (x+1)
kdp

● Depropagation has larger S

● ∵TS term increases with T
∴T  increase; kdp  increase

● At T = Tc
(i.e. ceiling temperature)
 Rp = Rdp
 6.8 Copolymerization.
Self-propagation / cross-propagation

in steady-state,
k11
M1 + M1 M1 [M1] and [M2] remain constant
k12
M1 + M2 M2 M1  M2 and M2  M1
k21
M2 + M1 M1 proceed at equal rate
k22
M2 + M2 M2  k12 [M1][M2] = k21[M2][M1]

Rate of disappearance of M1 and M2

 B. Kinetics of copolymerization.

 d [ M 1]
 a.   k 11[ M 1][ M 1]  k 21[ M 2][ M 1]
  dt
b.   d [ M 2]
 k 12[ M 1][ M 2]  k 22[ M 2][ M 2]
  dt
c. let, k 11 k 22 (reactivity ratio)
r1  and r 2 
  k 12 k 21
  steady state assumption.
    
 d. solving d [ M 1] d [ M 2]
     dt dt
  
k 12[ M 1][ M 2]  k 21[ M 2][ M 1]
: Copolymer equation or copolymer composition equation.
d[M1]/d[M2] : the molar ratio of the two monomers in the copolymer
[M1], [M2] : the initial molar concentration of monomers in the
            reaction mixture
d [ M 1] [ M 1]  r1[ M 1]  [ M 2] 
  
d [ M 2] [ M 2]  [ M 1]  r 2[ M 2] 
B. Kinetics of copolymerization.

d[M1]/d[M2]: molar ratio of repeat units in copolymer

[M1]/[M2]: molar ratio of monomers in initial feed
r1 = k11/k12 ; r2 = k22/k21

r1  1 M1 tends to self-propagate
r1  1  copolymerization is preferred

● Knowing r1 and r2  can project the desired d[M1]/d[M2]

(for conversion 10%)
● f1 and f2: molar fractions of M1 and M2 in the initial feed
 F1 and F2: molar fractions of M1 and M2 in the final copolymer
B. Kinetics of copolymerization.

The copolymer equation can be rewritten

Determination of reactivity ratios 

(1) Prepare copolymers using a range of monomer feed ratios

(2) Stop the polymerization at the early stages
(3) Determine the repeat unit ratios of the copolymers
B. Kinetics of copolymerization.
 C. Significance of reactivity ratio (r1, r2).
(1) r1 = r2 = 1

 truly random copolymer

F1 = f1 (curve A)
ethylene (M1)  vinyl acetate (M2)

r1 = 0.97, r2 = 1.02

(2) r1 = r2 = 0 

(i.e. k11= 0, k22= 0)

 truly alternating copolymer

F1 = 0.5 (curve B)
styrene (M1) maleic anhydride (M2)
r1 = 0.041 and r2 = 0.01

(3) 0 < r1 < 1, 0 < r2 < 1

(more common)  curve C

styrene (M1)  methyl methacrylate (M2)

r1 = 0.52, r2 = 0.46
 C. Significance of reactivity ratio (r1, r2).

(2) r1 = r2 = 0 • e.g. 60 oC
• St(r1=0.01)—maleic anhydride(r2=0)
(i.e. k11= 0, k22= 0)

 truly alternating copolymer

F1 = 0.5 (curve B)
2
styrene (M1) maleic anhydride (M2) 0.01 f1  f1 f 2
r1 = 0.041 and r2 = 0.01 F1  2 2
0.01 f1  2 f1 f 2  0  f 2
0.01 f1  f 2

0.01 f1  2 f 2
1

2

F1 ～ f1 plot
 C. Significance of reactivity ratio (r1, r2).
Azeotropic polymerization

● At cross point between curve C and the diagonal (i.e., f1 = F1)

● No change in [M1]/[M2] and d[M1]/d[M2] during the polymerization

d[M 1 ] [M 1 ]
∴ 
d[M 2 ] [M 2 ]

d [ M 1 ] [ M 1 ]  r1[ M 1 ]  [ M 2 ]   ∴ r1[ M 1 ]  [ M 2 ]
∵    1
d [ M 2 ] [ M 2 ]  [ M 1 ]  r2 [ M 2 ]  [ M 1 ]  r2 [ M 2 ]

r1[ M 1 ]  [ M 2 ]  [ M 1 ]  r2 [ M 2 ]
[ M 2 ](1  r2 )  [ M 1 ](1  r1 )

∴
[ M 1 ] 1  r2
 [St]/[MMA] = (1-0.46)/(1-0.52 ) = 1.125
[ M 2 ] 1  r1
 C. Significance of reactivity ratio (r1, r2).
Azeotropic polymerization

● At cross point between curve C and the diagonal (i.e., f1 = F1)

● No change in [M1]/[M2] and d[M1]/d[M2] during the polymerization
r1=0.6
Azeotrope r2=0.3
point
The azeotrope is important,
A particularly in industry, because the
monomer and copolymer composition
do not change with conversion, thus
producing copolymers homogeneous
in composition. Copolymerizations
under the other conditions will change
r1=0.5 the instantaneous compositions along
r2=0.5 the composition curve.

F1 ～ f1 plot
 C. Significance of reactivity ratio (r1, r2).
● For r1 > 1 and r2 > 1  azeotropic polymerization can also

happen, in principle, but never been observed in free

radical polymerization

(4) r1 >> 1, r2 << 1  curve D

styrene (M1)  vinyl acetate (M2)

r1 = 55, r2 = 0.01
styrene (M1)  vinyl chloride (M2)
r1 = 17, r2 = 0.02
(5) when r1r2 = 1  often referred as ideal copolymerization
● However, a random distribution of monomers only occurs
when r1 and r2 are both close to 1 2
f  f1 f 2
F1  2 1 2
● Methyl methacrylate (M1) and vinyl acetate (M2) f1  2 f1 f 2  f 2

r1 =10, r2 = 0.1 (r1r2=1) f1

  f1
f1  f 2
 curve E (instead of curve A)
 D. Alfrey-price Q-e scheme.
● A semiempirical relationship
● Express reactivity ratios in terms of characteristic constants of
each monomer
 Independent of comonomer

 Q1 
r1    exp[e1 (e1  e2 )] r1 = k11/k12 ; r2 = k22/k21
 Q2 
 Q2 
r2    exp[e2 (e2  e1 )]
 Q1 
Q1, Q2: measures of the reactivity of M1, M2
(related to resonance stabilization of monomer)
e1, e2: measures of the polarity of the monomers
 D. Alfrey-price Q-e scheme.
● Styrene (chosen as the standard): Q = 1.00, e = -0.80
● Q increase with resonance stabilization
 e is less negative with electron attracting substituent group
 D. Reactivity ratios
● Controlled by: steric / resonance / polar effects
● Steric effects: 1,2-disubstituted ethylene is difficult to form homopolymer
● Resonance effects: more stable intermediate easier to form
( less reactive in propagation)

(1) Styrene / vinyl acetate (r1 = 55, r2 = 0.01)

 ∵ styryl radical is much more stable than ethyl acetate radical
(2) Styrene / methyl methacrylate (r1 = 0.52, r2 = 0.46)
 ∵ styryl radical and methyl methacrylate radicals are similarly stable

• Polar effects: styrene / methyl methacrylate

the e-withdrawing methyl methacrylate or e-donating styrene
 increase the tendency of adding to the opposite member

H H CH3
CH2 C  CH2 C CH2 C
 OAc C O
OCH3
stable unstable stable
 E. Charge transfer complex polymerization
(alternating copolymer).
Theories: (1) polar effects in the TS (2) charge-transfer interactions
Maleic anhydride / styrene (r1  0 , r2  0)

maleyl radical

Polar effects 
involve resonance-stabilized
transition states

styryl radical
Regarding to formation of charge-transfer complexes
● shows characteristic UV max of the complex
● acts as a homopolymerization of the complex
● propagating chain end is a donor-acceptor (D-A) complex
(not a conventional radical, nor an ionic species)

Evidence favoring D-A complex

1. Reach maximum rate at 1:1 monomer feed

2. Alternation occur at all feed ratio
3. Fail to incorporate other added monomer
4. Rate enhanced by Lewis acids (by increasing acceptor property)
5. MW is hardly affected by any chain transfer agents
Regarding to formation of charge-transfer complexes

Other examples 

R R O
CH2 CH + CO CH2 CH C polyketones (6.57)
R R
CH2 CH + SO2 CH2 CH SO2 polysulfones (6.58)

● Both reactions tend toward alternation copolymerization

● SO2 and alkenes is known to form 1:1 complexes
● Possibly helped by polar effects in TS or charge transfer complex