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=
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
Semester 1 2007/2008 Fisika Polimer
Ariadne L. Juwono
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
Semester 1 2007/2008 Fisika Polimer
Ariadne L. Juwono
The polymerization rate: [ ] [ ] M I
k
fk
k R
1/2
1/2
t
d
p 0
|
|
\
|
=
Semester 1 2007/2008 Fisika Polimer
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
Semester 1 2007/2008 Fisika Polimer
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:
Semester 1 2007/2008 Fisika Polimer
Ariadne L. Juwono
Semester 1 2007/2008 Fisika Polimer
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
+
=
Semester 1 2007/2008 Fisika Polimer
Ariadne L. Juwono
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
Semester 1 2007/2008 Fisika Polimer
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
+
=
Semester 1 2007/2008 Fisika Polimer
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
Semester 1 2007/2008 Fisika Polimer
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
+
+ =
Semester 1 2007/2008 Fisika Polimer
Ariadne L. Juwono
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
Semester 1 2007/2008 Fisika Polimer
Ariadne L. Juwono
Semester 1 2007/2008 Fisika Polimer
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.
Semester 1 2007/2008 Fisika Polimer
Ariadne L. Juwono
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
=
|
\
|