Chapter 3 Radical Polymerization

Chapter 3 Radical Polymerization
3.1 Introduction Chain-growth polymerization

3.1 Introduction Radical polymerization
3.2 Chemistry of radical polymerization
Division of Chemistry & Biological Chemistry
School of Physical and Mathematical Sciences
Xing Yi LING, CBC, NTU
1
3.2.1 Initiation & the kinetics
3.2.2 Propagation & the kinetics
3.2.3 Termination & the kinetics
3.2.4 Chain Transfer
3.3 Kinetics of radical polymerization
3.3.1 Number-average degree of polymerization
(kinetic chain length)
2.1 Introduction
Polymerization
Step
polymerization
Chain growth
polymerization
Modern polymerization classification
polymerization polymerization
Radial
polymerization
Ioni
polymerization
Monomers are bifunctional units.
Long polymer chains are readily obtained from monomers e.g.
vinylidene compounds with general structure of CH
2
=CR
1
R
2
.
The special reactivity of -bonds in the carbon to carbon
double bonds make them susceptible to rearrangement if
double bonds make them susceptible to rearrangement if
activated by free-radical or ionic initiators.
Active center created by chain growth polymerization
propagates a kinetic chain, which leads to the formation of a
single macromolecules.
The reaction is stopped when the active center is neutralized
by termination reaction.
3
3 distinct stages of chain growth polymerization:
1. Initiation
when the active center is created. It acts as a chain carrier.
2. Propagation
involves growth of the macomolecular chain by a kinetic chain
mechanism.
mechanism.
It is characterized by a long sequence of identical events,
namely repeated addition of a monomer to the growing chain
3. Termination
The kinetic chain is brought to a halt by neutralization or
transfer of the active center.
4
Polymerization in chain-growth polymerization occurs only at the
reactive end of a growing chains.
The chain length increases rapidly from the early stage of
reaction.
Typically, the polymer formed from chain-growth has the same
chemical composition as the monomer.
chemical composition as the monomer.
Each unit in the chain is a complete monomer, and no residue.
5
Choice of initiators
Three general categories of initiators: free radical, cationic, and
anionic initiators.
Choice of the most appropriate initiators depends largely on the
group R
1
and R
2
in the monomer (CH
2
=CR
1
R
2
) and their effects on
the double bond.
It depends on the ability of the alkene -bond to react in a different
way with each initiator to produce either heterolytic (I) or homolytic
way with each initiator to produce either heterolytic (I) or homolytic
(II) fission.
!eterolyti
"I#
!omolyti
"II#
6
Choice of initiators
In most olefinic monomers of interest group R
1
is either H
or CH
3
. For simplicity, we can consider it to be H.
The group R
2
is classifiable as an electron-withdrawing
group,
+ -
In general, electron withdrawing substituents, -CN, -COOR,
-CONH
2
, reduce the electron density at the double bond, and
favor propagation by an anionic initiator.
+ -
7
Or, the group R
2
is classifiable as an electron donating group:
The electron donating groups tend to increase the double bond
nucleophilicity by donating electrons, such as alkenyl, alkoxyl, and
phenyl groups.
Electron donating groups encourage attack by cationic initiator.
+ -
Electron donating groups encourage attack by cationic initiator.
For homolytic initiator, the free radical is electrically neutral.
Therefore it is less selective and more generally used as initiator.
8
3.1 Introduction Radical Polymerization
Free radicals: independent existing species that possess an
unpaired electron
e.g. carbon-based free radical with sp
2
hybridization

Radical polymerization:
Most widely used and versatile
Polymerization for unsaturated monomers (with C=C bonds)
The bonds in the C=C makes them susceptible to
rearrangement if activated by free radicals or ionic initiators.
Almost all unsaturated monomers can be subjected to such form
of chain polymerization
9
3.1 Introduction
Radical polymerization:
Each polymer molecule grows by sequential additions of
molecules of unsaturated monomers to a terminal free-radical
reactive site, reactive centre
The growing chain radical attacks the -bond of a molecule of
monomer, causing it to break homolytically
The growth of the macromolecule is stopped when the active
centre is neutralized by a termination reaction.
centre is neutralized by a termination reaction.
New $ond to
the methylene
"C!
%
#
New ati&e
radial entre
tran'(erred to
the new hain
end
10
3 basic reaction stages in radical polymerization
1. Initiation when active center is created
2. Propagation involving growth of polymer chain,
characterized by the repeated addition of monomer to
growing chain
3. Termination the chain growing is brought to a halt by
neutralization or transfer of the active center.
neutralization or transfer of the active center.
Used widely for polymerization of the following monomers:
CH
2
=CR
1
R
2
,
CH
2
=CXY (1,1-disubstituted monomer),
CHX=CHY (1,2-disubstituted monomer).
11
1. Initiation
2. Propagation
3. Termination
3.2.1Initiation
Involves creation of free-radical active centre
Step 1: formation of a free radicals (R
) from an initiator
Step 2: addition of one of these free radicals to a molecule
of a monomer


= +

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
(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.

/+rther $rea.down
16
1. Homolysis scission
Photolysis homolysis by action of radiation
Use of photochemical initiator that decompose efficiently when exposed
to ultraviolet radiation.
Formation of free radicals begins at the instant of exposure, and
ceases as soon as the light source is removed.
h
3.2.1 Initiation
Benzophenone Benzoyl Phenyl
radial radial
Benzoin al.yl Benzoyl ,l.o*y$enzyl
ether radial radial
"R 0 al.yl#
h
17
3.2.1Initiation
Step 1: Formation of a free radical from an initiator
2. Single-electron transfer process
Redox reactions
Used for radical polymerization at low temperature (T < 50
o
C)
Same can be apply for all peroxide and hydroperoxide
R-O-O-R + Fe
2+
R-O + RO
-
(alkoxide ion) + Fe
3+
Or, Use of Co
2+
R-O-O-R + Co
2+
R-O + RO
-
+ Co
3+
C+myl
hydropero*ide
/erro+'
ion
C+mylo*y
radial
!ydro*yl
ion
/erri
ion
18
3.2.1Initiation
2. Single-electron transfer process
Redox reactions
Inorganic redox system
e.g.
Per'+lphate
ion
Bi'+lphite
ion
S+lphate
ion
S+lphate
radial1ion
Bi'+lphite
radial
19
3.2.1 Initiation
Step 2: Addition of one of these free radicals to a molecule of a
monomer
Active centre is created. The free radical R attacks the -bond of a
molecule of monomer via the same chemistry of monomer addition.
"I#
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
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 ] [

I
For redox systems:
For photochemical initiation:
Where = quantum yield
I
abs
= the intensity of the light absorbed
] ][ [
] [
Red Ox k
dt
I d
=

abs
I
dt
I d
'
] [
=
22
6*ample-
Cal+late the hal(1time o( $enzoyl pero*ide in $enzene at 77
o
C gi&en that the rate
oe((iient k
d
(or di''oiation o( thi' initiator +nder the'e ondition' i' 8 )4
17
'
1)
9 :hat
will $e the hange in initiator onentration a(ter ) ho+r at 77
o
C; Comment on the &al+e'
o$tained9
3.2.1 Initiation the kinetics
Rate R
i
of formation of active centers:
I
2 R
k
d
( 0 Initiator e((iieny
.
d
0 Rate oe((iient (or
initiator di''oiation
[ ] I k f
dt
R d
R
d i
2 == =
] [
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
26
3.2.2 Propagation
!ead1to1tail addition
(I)
(II)
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.
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
Rate of consumption of monomer:
If [M
] is the total concentration of all radical species, i.e.

[ ]
=
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
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
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.
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.
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
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
Or:
Chain radical abstract T (often H or halogen) from TA by
homolytic scission to yield a dead polymer molecule and
radical A
.
37
3.2.4.1 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
Type 2: Chain transfer to monomer, e.g. vinyl acetate
t1$+tyl pero*ide
S.eletal
'tr+t+re o(
the polymer;
38
3.2.4.1 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
Type 4: Chain transfer to transfer agent, e.g. carbon tetrabromide
39
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.
3.2.3.2 Chain transfer to polymer
Major effect on skeletal structure and properties of polymers
Formation of branched polymer molecules
40
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)
41
Type 2: Intermolecular chain transfer
e.g. polyethylene
42
e.g. poly(methyl methacrylate)
H abstraction from tertiary
C-H backbone
Tertiary radical is more
Tertiary radical is more
stable
43
e.g. Poly(vinyl acetate)
Product radical from H-
abstraction at a methyl group
is stabilized by electron
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
] = 0, the reaction is under steady state

R
i
0 R
t
2 1
2
2
/
]
] [ ] [
=
=

t i
k R
dt
d
dt
d
[M
M R
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
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
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
+
=
+
=
+

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
= =
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
=
( )
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
53
54
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
, respectively. Show that the manner of plotting used in the figure

(in next page) is consistent with the integrated first-order rate law.
Evaluate k
d
.
Evaluate k
d
.
azo$i'i'o$+tyronitrile
56
-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.
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
Calculate the initiator efficiency. The number-average molecular

weight of this polymer was found to be 390,000. Establish whether
the termination reaction takes place by combination or
disproportionation of growing chains.
806 17
7019
1
. min / log +
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
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

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3.1 Introduction Chain-growth polymerization

Xing Yi LING, CBC, NTU

Xing Yi LING, CBC, NTU

Xing Yi LING, CBC, NTU

Xing Yi LING, CBC, NTU

] is the total concentration of all radical species, i.e.

] = 0, the reaction is under steady state

, respectively. Show that the manner of plotting used in the figure

Calculate the initiator efficiency. The number-average molecular

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