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Chapter 3 Radical Polymerization - LN
Chapter 3 Radical Polymerization - LN
) from an initiator
Step 2: addition of one of these free radicals to a molecule
of a monomer
Xing Yi LING, CBC, NTU
= +
CHY RCH CHY CH R
R Initiator
"Step )#
"Step %#
13
3.2.1 Initiation
Step 1: Formation of a free radical from an initiator
Two principal ways to form free radicals:
(1) Homolysis scission
Chemical dissociation of a single bond, in which the two bonding
electrons go one each other onto the two atoms associated with the
original bond
Xing Yi LING, CBC, NTU
(2) Single-electron transfer process
Transfer of a single electron to or form an ion or molecules (e.g. in
redox reactions)
14
3.2.1 Initiation
Step 1: Formation of a free radicals from an initiator
1. Homolysis scission
Thermolysis
Bond scission upon heat (),
Many compounds contain weak bond which undergo thermolysis at useful
rate > 50
o
C.
Pero*ide
gro+p
,zo gro+p
R
)
and R
%
- an $e aromati, al.yl, or !
15
3.2.1 Initiation
1. Homolysis scission Thermolysis
Peroxides (ROOR) and hydroperoxides (ROOH) are most widely used.
They are thermally unstable and decompose into radicals at a
temperature.
Most commonly used peroxide: benzoyl peroxide
e.g.
"I#
Xing Yi LING, CBC, NTU
Mode (I) predominates because the attack at the methylene (CH
2
)
carbon is less steric hindered, and yield a product radical that is more
stable.
"II#
20
3.2.1 Initiation
Not all radicals forms from initiators are to react with
monomer. Some are lost in side reactions.
e.g. Induced decomposition
Xing Yi LING, CBC, NTU
2o not ta.e part in the polymerization reation33
The e((iieny o( initiator may not $e )445
21
3.2.1 Initiation the kinetics
For peroxides and azo compounds:
Where k
d
= rate constant for homolytic decomposition of initiator
[I] = concentration of initiator
2
] [
] [
I k
dt
I d
R I
d
=
Rate of consumption of Initiator
dt
I d ] [
] [
radicals decomposed of ion Concentrat
radicals reactive of ion Concentrat
= f
initiator by formed Radicals
polymer into ed incorporat Radicals
=
3.2.2 Propagation
Growth of polymer chain by rapid sequential addition of
monomer to the active centre
Duration of each monomer addition: ~ milisecond; hence
several thousands of addition within a few seconds
Xing Yi LING, CBC, NTU
26
3.2.2 Propagation
!ead1to1tail addition
(I)
(II)
Xing Yi LING, CBC, NTU
Mode (I) Head-to-tail addition dominates.
If head-to-head addition occurs, it will followed immediately by a
tail-to-tail addition to generate a more stable active centre, which
will continue to propagate via head-to-tail addition.
!ead1to1head addition
Why?
27
3.2.2 Propagation
Mode (II) only contributes significantly for the few monomers, for
which X is small (similar size to H atom).
For general description of radical polymerization, it is reasonable to
neglect mode (II), and assume propagation proceeds exclusively by
mode (I) head-to-tail addition.
Xing Yi LING, CBC, NTU
28
3.2.2 Propagation the kinetics
Propagation:
Assume rate of coefficient k
p
for propagation is independent of the length of
the growing chain:
Given that long-chain polymer molecules are formed
Amount of monomer consumed in the initiation stage is negligible to that
consumed by propagating chains
+
1
M M M
i
k
i
p
Xing Yi LING, CBC, NTU
Rate of consumption of monomer:
If [M
=
i
i
M M
1
] [
] ][ [
] [
= = M M
M
p p
k
dt
d
R
( ) .. ] [ ... ] [ ] [ ] [
] [
... ] ][ [ ... ] ][ [ ] ][ [
] [
+ + + + =
+ + + + =
i p
i p p p
k
dt
d
k k k
dt
d
M M M M
M
M M M M M M
M
2 1
2 1
29
3.2.3 Termination
The active centre is destroyed irreversibly and propagation
ceases.
Chain termination can take place by:
1. Combination/ coupling
interaction of two active chain ends
most common route
Xing Yi LING, CBC, NTU
2. Disproportionation
interaction of an active chain end with an initiator radical
30
3.2.3 Termination
Type 1: Combination
Coupling together two growing chains to form a single polymer molecule
Xing Yi LING, CBC, NTU
Single dead polymer molecule (with degree of polymerization = x + y)
Radical coupling reaction at head-to-head linkage, with initiator
fragment (the R groups) at both chain ends
31
3.2.3 Termination
Type 2: Disproportionation
Abstraction of a hydrogen atom from the penultimate C atom of one
growing chain radical by another,
And the remaining electron from the C-H bond joining the unpaired
electron on the terminal C atom to form a terminal -bond.
Xing Yi LING, CBC, NTU
2 dead polymers are formed, with degree of polymerization x and y
respectively.
One with saturated end group, the other with unsaturated end group.
both with an initiator fragment at the other chain end.
32
3.2.3 Termination
Depends on the monomer and polymerization conditions.
Polystyrene, poly vinyl (CH
2
=CHX) chain radicals terminate
mainly by combination.
Poly(methyl methacrylate), -methylvinyl (CH
2
=C(CH
3
)X) chain
radical terminate dominantly by disproportionation, especially T >
60
o
C.
Xing Yi LING, CBC, NTU
For poly(methyl methacrylate), X =
33
6*ample-
:rite down a reation 'heme (or polymerization o( 'tyrene initiated $y thermoly'i' o(
azo$i'i'o$+tyronitrile, inl+ding $oth om$ination and di'proportionation a' po''i$le
mode' o( termination9
3.2.3 Termination the kinetics
Termination
Rate of consumption of radicals:
k
tc
- rate o( oe((iient' (or om$ination
k
td
- rate o( oe((iient' (or
di'proportionation
[ ][ ] [ ][ ]
+ = M M 2 M M 2
M
td tc
k k
dt
d ] [
+
j i
M M
j i
P
+
j j
P P +
tc
k
td
k
Xing Yi LING, CBC, NTU
Rate of polymerization:
Bea+'e % growing hain' are $eing on'+med $y
eah termination
:here k
t
0 k
t
< k
td
2
] [
] [
+
= M k
dt
P d
tc
j i
2
] [ 2
] [
=
+
M k
dt
P P d
tc
j i or
dt
2
] [M 2
M
= =
t t
k
dt
d
R
] [
36
3.2.4 Chain transfer
The active centre is transferred from the active chain to
another species in the polymerization
Xing Yi LING, CBC, NTU
Or:
Chain radical abstract T (often H or halogen) from TA by
homolytic scission to yield a dead polymer molecule and
radical A
.
37
3.2.4 Chain transfer
3.2.4.1 Chain transfer with small molecules
Chain transfer can occurs with molecules of initiator, monomer, solvent,
and deliberately added transfer agent.
Chain transfer reaction leads to death of a propagating chain
Type 1: Chain transfer to initiator, e.g. peroxide
Xing Yi LING, CBC, NTU
Type 2: Chain transfer to monomer, e.g. vinyl acetate
t1$+tyl pero*ide
S.eletal
'tr+t+re o(
the polymer;
38
3.2.4 Chain transfer
3.2.4.1 Chain transfer with small molecules
Type 3: Chain transfer to solvent, e.g. toluene
Type 4: Chain transfer to transfer agent, e.g. carbon tetrabromide
Xing Yi LING, CBC, NTU
Type 4: Chain transfer to transfer agent, e.g. carbon tetrabromide
39
3.2.4 Chain transfer
Free radical is NOT destroyed in the chain transfer reaction; it is
merely transferred.
The process terminates the chain, but at the same time generates a
new radical. If the new species is sufficiently active, another chain
will emanate from the new center.
Chain transfer results in lower molar mass of polymer product.
Xing Yi LING, CBC, NTU
3.2.3.2 Chain transfer to polymer
Major effect on skeletal structure and properties of polymers
Formation of branched polymer molecules
40
3.2.4 Chain transfer
Type 1: Intramolecular chain transfer (back-biting reactions)
- Short chain branches; e.g. polyethylene, produced by high-pressure
free radical polymerization.
- Formed by backbiting involving 5- or 6- membered cyclic transition
states.
Lower degree of crystallinity (~ 45% onwards)
Lower melting point (105 115
o
C, Compared to linear polyethylene (135
140
o
C)
Xing Yi LING, CBC, NTU
41
3.2.4 Chain transfer
3.2.4.2 Chain transfer to polymer
Type 2: Intermolecular chain transfer
e.g. polyethylene
Xing Yi LING, CBC, NTU
42
3.2.4 Chain transfer
3.2.4.2 Chain transfer to polymer
Type 2: Intermolecular chain transfer
e.g. poly(methyl methacrylate)
H abstraction from tertiary
C-H backbone
Tertiary radical is more
Xing Yi LING, CBC, NTU
Tertiary radical is more
stable
43
3.2.4 Chain transfer
3.2.4.2 Chain transfer to polymer
Type 2: Intermolecular chain transfer
e.g. Poly(vinyl acetate)
Product radical from H-
abstraction at a methyl group
is stabilized by electron
Xing Yi LING, CBC, NTU
is stabilized by electron
delocalization with carbonyl -
bond
44
State the differences between step and chain polymerization.
6*ample-
45
3.3.1 Rate of polymerization
At Steady state,
Rate of radical formation Rate of [M
] loss by termination
The net of change of [M
t i
k R
dt
d
dt
d
[M
M R
Xing Yi LING, CBC, NTU
The steady-state rate of polymerization
2 1
2
/
] [
t
i
k
R
M
[ ]
2 1
2
/
] [
= =
t
i
p p
k
R
k
dt
d
R M
M
47
3.3.1 Degree of polymerization
Number-average degree of polymerization
n
x
/ ] [ / ] [
+
+ +
=
=
dt P P d dt P d
/dt d
x
j i j i
n
[M]
time unit in formed polymer of Moles
time unit in consumed monomer of Moles
Xing Yi LING, CBC, NTU
2 2
] [ 2 ] [
] ][ [
/ ] [ / ] [
+
+
=
+ +
M k M k
M M k
dt P P d dt P d
td tc
p
j i j i
48
2 / 1
2
] [ /
= =
t
i
t td
k
R
k k q M and Q Q
( )
) 1 ( ] [
] [
t
p
n
q k M
M k
x
+
=
o
In a$'ene o( hain tran'(er
3.3.1 Degree of polymerization
Number-average degree of polymerization
2 / 1 2 / 1
2 / 1
) 2 / ( ) 1 (
] [
) 2 / )( 1 (
] [
) 1 ( ] [
i t
p
t i t
p
t
R k q
M k
k R q k
M k
q k M
+
=
+
=
+
3.3.1 Degree of polymerization
Kinetic chain length,
The average number of repeat units added to a single chain radical prior
to termination.
/ ] [ dt d
/dt d
M
[M]
n terminatio of rate
n propagatio of rate
=
=
= Steady
'tate-
i
p
t
p
R
R
R
R
= =
Xing Yi LING, CBC, NTU
2 / 1 2 / 1
2
) 2 / ( 2
] [
] [ 2
] [
] [ 2
] ][ [
/ ] [
i t
p
t
p
t
p
R k
M k
M k
M k
M k
M M k
dt d
M
=
=
=
[ ]
[ ] ( )
2 / 1
2 I k k f
M k
d t
p
=
"R
i
0 % f .
d
>I?#
" >@
? 0 "R
i
A% .
t
#
)A%
#
50
( )
2 / 1 2 / 1
) 2 / ( ) 1 (
] [
i t
p
n
R k q
M k
x
+
=
o
( )
= x
2
2 / 1 2 / 1
) 2 / ( 2
] [
i t
p
R k
M k
=
3.3.1 Degree of polymerization
( )
o
+
=
q
x
n
1
2
( ) =
o
n
x
( ) 2
o
=
n
x
Termination i' e*l+'i&ely $y
di'proportionation
Termination i' e*l+'i&ely $y
om$ination
t td
k k q / = Q
0 (ration o( termination reation' that i' proeeded $y di'proportionation
6*ample-
"a# Cal+late the onentration o( $enzoyl pero*ide reB+ired to prepare poly'tyrene with
n+m$er1a&erage molar ma'' o( CD4 .g mol
1)
$y $+l. polymerization at 74
o
C9 ,''+me "i#
the initiator i' 74 5 e((iientE "ii# the rate oe((iient' (or initiator di''oiation,
propagation, and termination' are %)4
17
'
1)
, FG) dm
F
mol
1)
'
1)
, and G )4
C
dm
F
mol
1)
'
1)
,
re'peti&elyE "iii# the den'ity o( 'tyrene at the polymerization temperat+re i' 4988 g m
1
F
E and "i&# that termination $y di'proportionation, and hain tran'(er to initiator and
monomer, are negligi$le9
"$# Cal+late initial &al+e' o(
"i# The radial onentration and
"ii# The rate o( $+l. polymerization e*peted (or $+l. polymerization o( 'tyrene at the "ii# The rate o( $+l. polymerization e*peted (or $+l. polymerization o( 'tyrene at the
onentration o( $enzoyl pero*ide determined in "a#9
Xing Yi LING, CBC, NTU
53
Xing Yi LING, CBC, NTU
54
Xing Yi LING, CBC, NTU
55
Chapter 3 Exercises
Q 3.1
The decomposition of azobisisobutyronitrile (AIBN) in xylene at 77
o
C was studied by measuring the volume of N
2
evolved as a
function of time. The volumes obtained at time t and t = are V
t
and
V
-0.4
-0.2
0.0
0.2
L
o
g
(
1
-
V
t
/
V
)
F9) "Contin+ed#
0 50 100 150 200 250 300 350
-0.8
-0.6
L
o
g
(
1
-
V
Time (min)
Q 3.2
Write down the mechanism for the free radical polymerization of
vinyl-acetate initiated by 2,2-azobis(2,4-dimethylpentanenitrile)
in ethyle acetate including (a) initiation, (b) propagation, and (c)
termination by disproportionation.
Xing Yi LING, CBC, NTU
58
Q 3.3
14.45 g of methyl methacrylate were polymerized at 50
o
C for 55
min using 0.2096 g of ,-azobisisobutyonitrile (AIBN) as initiator,
to give 1.6826 g of polymer. Radioactivity assay indicated that the
polymer sample contained 7.07 10
-4
g of azobisnitrile.
Consider that the first-order rate constant for the decomposition of
AIBN is given by:
7019
T
k
Q 3.4
Consider the free-radical polymerization of methyl methacrylate in
toluene solution at 77
o
C, initiated by azobisisobutyronitrile (AIBN).
When the initial monomer concentration was 2.07 M and the initial
AIBN concentration was 2.11 x10
-4
M, the initial rate of polymerization
was determined to be R
p
= 2.49 x10
-3
M min
-1
.
(a) Determine the initial rate of initiation (R
i
), and k
p
/(k
t
) by
considering that the rate constant for the decomposition of AIBN at
Xing Yi LING, CBC, NTU
considering that the rate constant for the decomposition of AIBN at
77
o
C is k
d
= 5.7x10
-3
min
-1
, and that virtually all radicals are
capable of initiating chains.
(b) Determine the initial kinetic chain length and the expected number-
average molar mass assuming only termination mainly takes place
by combination.
60
Q 3.5
The e((iieny o( ,IBN in initiating polymerization at 74
o
C wa' determined $y
the (ollowing 'trategy9 They mea'+red R
p
and , and calculated R
i
= R
p
/.
The constant k
d
was measured directly in the system, and from this
quantity and the measured ratio R
p
/, the fraction f could be
determined. The following results were obtained from different
concentration of initiator:
[I] g!"# R
p
/ (mol L
-1
s
-1
)
494DD7 49FCC 10
-8
494DD7 49FCC 10
-8
49%D4 )9DC 10
-8
49%D4 )9C% 10
-8
)944 79CC 10
-8
)9D4 )49H 10
-8
%9D4 )C9) 10
-8