Chapter 3. Chain-Growth (Addition) Polymerization

Semester 1 2007/2008
Chapter 3. Chain-growth (addition)

polymerization
3.1. Free-radical polymerization
3.2. Kinetics of chain-growth polymerization
3.3. Molecular weight and its distribution
3.4. Effects of temperature and pressure on
chain polymerization
Semester 1 2007/2008 Fisika Polimer
Ariadne L. Juwono
The polymerization of unsaturated monomers typically involves
a chain growth polymerization.
Chain-growth polymerizations require the presence of an
initiating molecule that can be used to attach a monomer molecule
at the beginning of the polymerization.
These 3 types of polymerization share 3 common steps:
Initiation,
Propagation and,
Termination.
The initiating species (initiator) may be a radical, anion, and cationic.
One act of initiation may lead to the polymerization of thousands of
monomer molecules. Thus polymer molecules are formed from the
beginning, and almost no species intermediate between monomer
and high-molecular-weight polymer are found.
3.1. Free-radical polymerization & copolymerization
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Initiation
Initiation consists of 2 steps:
a. Dissociation step: the initiator forms two radical species.
The labile bond can be broken by heat of irradiation (uv, gamma).
b. Association step: addition of a single monomer molecule to the
initiating radical.
A free-radical polymerization has 3 main steps:
Initiation of the active monomer,
Propagation or growth of the active chain by sequential addition of
monomers,
Termination of the active chain to give the final polymer product.
3.2. Kinetics of free-radical polymerization
Ariadne L. Juwono
I-I 2I
k
d
k
d
= A exp (-E
a
/RT),
where: k
d
is the dissociation rate-constant,
E
a
is the activation energy for dissociation
Dissociation
Example
benzoyl peroxide
2,2-azobis(isobutyronitrite) (AIBN) cyanoisopropyl radicals
Ariadne L. Juwono
Association
I + M IM
k
a
k
a
is the monomer association
rate constant
Example
benzoyl peroxide
styrene
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Propagation
A process of monomer units addition to the initiated monomer species.
Additional monomers are added sequentially during subsequent
propagation steps.
Propagation continues until termination process occurs
I M + M IM
k
p
I M
x
+ M IM
x
M
k
p
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Termination
Termination occurs when 2 propagating radical chains of arbitrary
degrees of polymerization of x and y meet their free-radical ends.
There are 3 mechanisms of termination:
1. Combination
2. Disproportionation
3. Chain transfer
Ariadne L. Juwono
Combination
To give a single terminated chain of degree of polymerization x + y
through the formation of a covalent bond between the 2 combining
radical chains.
I M
x-1
M + MM
y-1
I IM
X-1
M M
y-1
I
k
tc
Example: termination by combination of styrene polymerization
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Disproportionation
One terminated chain will have an unsaturated carbon group while
the other terminated end is fully saturated.
I M
x-1
M + MM
y-1
I I M
X
+ I M
y
k
td
Example
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Chain transfer
To give hydrogen abstraction from an initiator, monomer, polymer,
or solvent molecule.
I M
x-1
M + SH I M
X-1
MH + S
k
tr
Example
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Ariadne L. Juwono
The rate constants vary in a wide range, because they depend on the
reactivity of both the radical and the monomer.
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Free-radical polymerization kinetics
I M
x
+ M IM
x
M
k
p
Assumption: the propagation step has equal reactivity with other steps
R
o
R
p
= k
p
[I Mx ] [M]
Where: R
o
= the overall rate of polymerization in a free-radical pol,
R
p
= the rate of chain propagation
The propagation rate for free-radical poln is very rapid. Typical condition,
a polymer having mol weight of 10 million can be formed in only 0.1 s.
Problem: the radical concentration is normally not known.
Solution: assuming that the total radical population obtains a steady-state
concentration over the most of the poln process.
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The steady-state condition:
the radicals are formed in the initiation step = the radicals are consumed
in the termination step.
Ri Rt
The overall rate of initiation is controlled by the slower step, which is
the dissociation of the initiator.
[ ]
[ ] I 2k
dt
I d
R
d i
=
=
where: [I] = concentration of the free radical,
[I] = the concentration of the initiator,
2 radicals are produced in each dissociation step.
[ ]
[ ] I 2fk
dt
I d
R
d i
=
=
where: f = fraction of effective initiator-radicals (0.3 0.8).
Some initiator-radicals may recombine with other radicals
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At this stage, consider only termination by combination and
disproportionation so that :
I M
x
+ I M
x
P
k
t
where: P is the deactivated polymer,
k
t
is the termination rate constant (k
t
= k
tc
+ k
td
)
[ ]
[ ]
2
x t
x
t
IM 2k
dt
IM d
R =
=
[ ] [ ]
1/2
1/2
t
d
x
I
k
fk
IM
|
|
\
|
=
The termination rate equation:
The steady-state condition:
Remember that R
o
R
p
= k
p
[I Mx ] [M]
[ ] [ ] M I
k
fk
k Rp
1/2
1/2
t
d
p
|
|
\
|
=
The propagation rate equation:
,so that
Ariadne L. Juwono
The polymerization rate: [ ] [ ] M I
k
fk
k R
1/2
1/2
t
d
p 0
|
|
\
|
=
Ariadne L. Juwono
The ratio of rate constant is a useful information about the thermo-
chemistry of polymerization and is a function of temperature.
If the rate constant for initiator decomposition and the initiator efficiency
Are known, the ratio of rate constant can be evaluated.
The ratio of rate constant
2
i
2
p
t
2
p
[M] R
2R
k
k
=
|
|
\
|
t
2
p
k
k
Ariadne L. Juwono
The number-average degree of polymerization at any time:
t
p
n
R
R
X =
In steady-state:
[ ]
[ ]
1/2
d t
p
n
) I fk 2(k
M k
X =
Consider termination by combination, disproportionation, and chain
transfer:
tr td tc
p
n
R R R
R
X
+ +
=
The rate of termination by chain transfer: R
tr
= k
tr
[IM
x
] [SH]
|
\
|
+ =
[M]
[SH]
C
) X (
1
X
1
0 n n
p
tr
k
k
C =
The chain-transfer coefficient:
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Ariadne L. Juwono
3.3. Molecular weight and its distribution
A case in vinyl polymers
These polymers have the same average molecular weight throughout
the reaction.
Assume that the terminations is by disproportionation of transfer.
Define:
p : the prob of a growing chain radical will propagate rather than
terminate.
p
x-1
(1-p) : the prob of formation of an x-mer as a result of (x-1)
propagation and termination.
t p
p
R R
R
p
+
=
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Define
N = the total number molecules in the system,
N
0
= the initial number of initiator.
x
n
= the number-average degree of polymerization
p 1
1
c
c
N
N
x
0 0
n
= = =
N
0
is the total number of units present and N = N
0
(1-p)
1 x 2
0 x
p p) - (1 N N

=
w
x
is the weight fraction of x-mers
1 x 2
0
x
x
p p) x(1
N
xN
w

= =
The weight-average degree of polymerization:
p 1
p 1
x
w
+
=
Similar to step polymerization
Ariadne L. Juwono
In a case when a high polymer is formed, p ~ 1 and x
w
/x
n
= 2.
In the case of termination by combination with the absence of
transfer, x
w
/x
n
= 1.5 (f = 2).
The meas of x
w
/x
n
would differ between the possibilities of
termination by combination and by disproportionation.
difficult !!
A method is to measure the number of initiator fragments per
molecule of polymer.
2 x
x
p) (ln xp w =
p ln
1 -
x
n
=
p ln
2
x
w
=
In general distribution function by Zimm (1948)
y z
1 Z
x
e x
z!
y
w
|
|
\
|
=
+
y
z
x
n
=
y
1 z
x
w
+
=
Ariadne L. Juwono
In a case of autoacceleration in the polymerization of methyl
methacrylate, x
w
/x
n
~ 10, p > 0 and < 1.
When chain transfer involves, the distribution of molecular weights
has a long, high-molecular-weight tail. The empirical function:
2
yx z
1 z
x
e x y
1 z
w

+
(
(
(
(
|
|
\
| +
=
1
n
y
1 z
x
|
|
\
| +
=
|
|
\
| +
|
|
\
| +
=
1 z
y
2 z
1
w
Ariadne L. Juwono
For low-molecular-weight polymers, the empirical distribution function
is called the logarithmic normal distribution (Lansing, 1935)
2
2
0
2
2
) lnx (lnx
0
2
e
x
1

e
w(x)
=
2
0 n
2
e x x =
2
3
0 w
2
e x x =
Other empirical equations were proposed by Wesslau (1956), Tung (1956),
Gordon (1961), and Roe (1961)
For extremely narrow-molecular-weight polymers, the empirical distr
function is described by Possion distribution (Flory, 1940)
1)! (x
xe
1
w(x)
2 x
+
=

1 x
n
+ =
2
n
w
1) (

1
x
x
+
+ =
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The Gibbs free energy of polymerization: G
p
= H
p
T S
p
where: Hp is the heat of polymerization, H
p
E
p
- Ed
p
(neg)
E
p
and E
dp
are the activation energies for propagation and
depolymerization respectively,
S
p
is the entropy of polymerization (neg).
For low temp polymerization, both H
p
and S
p
are negative and
G
p
is also negative. As the temperature increases, G
p
become
less negative.
At certain temperature, the polymerization reaches equilibrium (rate
of polymerization = rate of depolymerization)
This temp is called the ceiling temperature (Tc).
G
p
= 0
p
p
c
S
H
T =
3.4.1. Free-radical polymerization thermodynamics
3.4. Effects of temperature and pressure on chain polymerization
Ariadne L. Juwono
Ariadne L. Juwono
The expression of the rate of propagation or the overall polymerization
rate by Arrhenius-type equation:
RT
E
p p
p
e A k
=
where: A
p
is the collision frequency factor
for propagation,
E
p
is the energy of activation for
propagation
The rate-constant ratio:
RT
2
E
Ep
t
p
t
p
t
e
A
A
k
k

|
|
\
|
=
Graph log (k
p
/k
t
) vs 1/T (E
p
E
t
) and (A
p
/ A
t
) can be evaluated.
For most polymerization:
The increase in (k
p
/k
t
) ~ 30 35% for every 10 C near RT
(E
p
E
t
) ~ 20 25 kJ/mole.
For most monomers:
E
p
~ 30 kJ/mole, E
t
~ 12 - 20 kJ/mole.
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3.4.2. Effect of pressure on free-radical polymerization
Polymerization of styrene at high pressure (3000 atm) :
The rate of dissociation of initiator <, the rate of polymerization >,
The rate of overall polymerization 7 8 X >, the rate of termination <,
The molecular weight >>
Eyring rate theory:
V
P
RTlnK
T
=
|
\
|

Chapter 3. Chain-Growth (Addition) Polymerization

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