Overview of the course

The establishment of polymer science and molecular

weight characterization techniques. (Chapter 1 and 2)

Condensation polymerization and step growth

polymerization. (Chapter 3)

Addition polymerization and chain growth

polymerization. (Chapter 4, 5, 6, 7)

Polymerization for molecular weight control and

stereo-structure control (Chapter 5, 6, 7)
Comparison of different chain growth polymerization
Initiation Active Propagation Termination Transfer
systems species (calculation)
1 AIBN; BPO Radical Xn, Xw, PDI Coupling Transfer
[M] Disproportionati agents
uncertain on Inhibition;
retardation
2 Sodium Anion/ Xn, Xw, PDI -hydride No transfer
naphthalene; conunterion [I] = [M-] elimination
n-BuLi
3 AlCl3/tert- Cation/ Non-living, Spontaneous Polymer to
butyl chloride; counterion (radical Termination monomer
BF3/HF; system) Combination Monomer to
BCl3/tert-butyl Living with the polymer
chloride; (anionic counterion Polymer to
Et2AlCl/tert- system) polymers
butyl chloride;
I2
4 AlEt2Cl/TiCl3 Coordination Stereocontrol N/A N/A
 Calculation for Mn, Mw, PDI

Radical polymerization Cationic polymerization Anionic polymerization

Termination and transfer reaction

Initiation, propagation and end groups

State-state assumption
Xn; Xw:

Xn = Number average Mpolymer/Mrepeat unit

Xw = Weight average Mpolymer/Mrepeat unit

PDI = Xw/Xn
Number average and weight average molecular weight
(Mpolymer):

1) Characterization: GPC, SLS, VPO, etc.

2) End group analysis

Number average Mpolymer = Mass of polymers/ # (polymer
chains)

In the case of living polymerization

Number average Mpolymer = Mass of polymers/I-fragments

In the case of cationic polymerization

End group analysis cannot be used for the evaluation of
molecular weight. Why?
 In the case of free radical polymerization
termination by coupling:
#(ends) = #(I-fragments) = 2 x # (polymer chains)

termination by disproportionation:
#(ends) = 2#(I-fragments) = 2 x # (polymer chains)

Number average Mpolymer = 2 x Mass of polymers/I-

fragments (100% coupling)

Number average Mpolymer = Mass of polymers/I-

fragments (100% disproportionation)
If 50% of the radical chains terminated by coupling and
50% disproportionation.

Number average Mpolymer = Mass of polymers/[(1/2)(50%

I-fragments) + 50% I-fragments]

Mass of the polymer is 2 g, the number of I-fragments

is 2 x 10-3 mol
Number average Mpolymer = 2/[(1/2)(50% 2 x 10-3) + 50% 2
x 10-3] = 1.3 x 103
 Xn from kinetic chain length

Rp Rp
Xn is proportional to the kinetic chain length
Ri Rt

Rp
Xn Free radical polymerization with coupling
Rt
Rtr
2

Rp Cationic polymerization (always has transfer,

Xn
Rt Rtr
but no coupling)
Free radical polymerization with
disproportionation
 Rp
Xn
Rt
Rtr
2
k p [ M ][ M ]
Xn
kt [ M ]2 ktr , M [ M ][ M ] ktr , I [ I ][ M ] ktr , S [ S ][ M ] ktr , XA[ XA][ M ]

Transfer to: monomer initiator solvent transfer agent

1 kt [M]2 k [M ][M] ktr,I [I][M] ktr,S [S][M] ktr,XA [XA][M]

= + tr,M + + +
Xn k p [M ][M] k p [M ][M] k p [M ][M] k p [M ][M] k p [M ][M]

1 Rt / 2 ktr , M ktr , I [ I ] ktr , S [ S ] ktr , XA [ XA]

Xn Rp kp k p [M ] k p [M ] k p [M ]
1 1 [I ] [S ] [ XA]
CM C I CS C XA
X n X n o [M ] [M ] [M ]
The Mayo Equation
 1 kt 1 kts 1 [S ]
CM C S
X n k p [M ] k p [M ] [M ]

Rt = kt[P+A-]

Rp = kp[P+A-][M]

1 1 [I ] [S ] [ XA]
CM C I CS C XA
X n X n o [M ] [M ] [M ]

1
2kt [M]2 k M
1
=2 = t
[ ] [M ]
f kd
[I ]
( Xn ) 0 k p [M ][M] k p [ M ] kt
 Disproportionation Coupling

Xn 2

Xn = X%D +(1-X%) (2)C

X: percentage of the final polymer chains terminated via disproportionation

10 chains with of 100:

All terminated via coupling: Xn = 200
All terminated via disproportionation: Xn = 100
50 % terminated by coupling and 50 % terminated by disproportionation:
total polymer chains = 25 + 50 = 75

Right: Xn = 200 x (25/75) + 100 x (50/75) = 200 x 0.33 + 100 x 0.67 = 132.67

Wrong: Xn = 200 x 50% + 100 x 50% = 150

No caculation for Xw and PDI from the kinetic chain length

 Xn from Probability Calculation

p = probability that a propagating radical continues to

propagate instead of terminating
Rp Rp
p Xn
R p Rtr Rt Rt Rtr
Disproportionation Coupling

1
Xn = Xn =
2
1- p 1- p

2+ p
1+ p Xw =
Xw = 1- p
1- p

PDI
Xw
1 p
Xw 2 p
PDI
Xn Xn 2
 When Xn is known, what kind of other information can
be calculated?
End group:
1) Number of I-fragments;
2) Number of polymers;
3) Number average molecular weight
4) percentage of the radicals terminated by different mode
Number average Mpolymer = Mass of polymers/[(1/2)(50% I-fragments) +
50% I-fragments]

Kinetic chain length:

1)
2) Xn
3) Percentage of the polymers obtained via different termination mode

= Rp/Rt
Xn = X% D +(1-X%) (2)C

From probability Calculation

 For example
GPC analysis reveals that a polystyrene sample has Mn of 1000 g/mol
and PDI of 1.8. Rp/(Rp + Rt) = 0.9
What is the Mw for the polymer?
What is the percentage of the radical species terminated via coupling?

Mw = Mn X PDI = 1000 x 1.8 = 1,800 g/mol

how the radical terminated can be derived from end group analysis, kinetic
chain length () calculation and probability calculation for PDI.

No end group and (Rp/Rt) information provided in the question. So PDI

information maybe useful to determine how the radical is terminated.

PDI = 1 + P (Disproportionation) PDI = 1 + P (coupling)

(1+P) radical % terminated via disproportionation + (1 + P) radical %

terminated via coupling = 1.8
P = Rp/(Rp + Rt) = 0.9
radical % terminated via disproportionation + radical % terminated via
coupling = 1
So
radical % terminated via coupling = [(p-0.8) x 2]/p = 22%
 Anionic and living cationic polymerization

For example:
What is the designed molecular weight when styrene
(100 mol) is initiated by n-butyl lithium (1 mol) and
sodium naphthalene (1 mol), respectively.
 Initiation systems

Understand the initiation reactions and function of

each system; e.g. whether BPO can be used for
cationic polymerization? which systems can initiate
living polymerization? what kind of monomers can
be polymerized for each system?

Be able to draw the initiation reactions.

 Radical
Tolerant to various functional groups;
Suitable for a broad range of monomers;
Easy bi-molecule termination;
Possible chain transfer

Cationic
Sensitive to impurity and moisture;
Free ion and ion pair, so polarity of solvent and counter ion influence the
polymerization rate
Limited number of monomers;
Cationic rearrangement; transfer, termination

Anionic
Sensitive to impurity and moisture;
Free ion and ion pair, so polarity of solvent and counter ion influence the
polymerization rate
Limited number of monomers;
Living

Ziegler-Natta
Metal coordination, so stereo-control
 Monomers

Suitability for each polymerization

Styrene technique
Butadiene, isoprene
MMA (Acrylates) Monomer addition mode
Acrylic acid
Possible side reactions existed for
Isobutylene each polymerization mechanism
Vinyl ether (those discussed in the teaching
slides)
Ethylene
Propylene Tg for the resulting polymers
 Chain transfer

Chain transfer terminates the propagating chain and starts a new chain,
so overall molecular weight will be smaller than the system without
transfer reactions.

The concentration of the active species remain constant, so the transfer

has no influence on the polymerization rate.

Chain transfer to solvent or monomers, a new chain starts to grow into

polymers without end groups from the initiator.

Cationic chain transfer reactions

 Block Copolymer

Living anionic polymerization

Living cationic polymerization

Radical polymerization X

Cationic polymerization X

Ziegler-Natta polymerization X