Chapter 2

CHAPTER 2
Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 27

2.1. INTRODUCTION CHAPTER 2
Chain reaction polymerization may be classified as free radical,

cationic, anionic or step-growth polymerization depend on the
nature of the reactive centers.
• In free radical polymerization, growing chain carriers free radical.

• Cationic polymerization, growing chain end carries carbonium
(positive charge).
• Ionic polymerization involves a growing chain end with a
carbanion (negative charge).
• Coordination polymerization is thought to involve the formation of
a coordination compound between the catalyst, monomer, and
growing chain.

2.2. FREE RADICAL POLYMERIZATION CHAPTER 2
2.2.1. Free radical mechanism of addition polymerization
Chain-reaction polymerization is the addition of unsaturated

monomers to a rapidly growing chain. The most common
unsaturated compounds that undergo chain reaction
polymerization are olefins
• The growing polymer in chain-reaction polymerization is a free

radical.
• The chain reaction polymerization involves three fundamental
steps: Initiation, propagation, and termination, may be has
chain transfer.

 Initiation:
Initiation may occur by absorption of heat, light, or high-energy
irradiation and the addition of small quantities of compounds
called initiators.
• Typical initiators include peroxides, hydroperoxides, azo
compounds, Lewis acids, and organometallic reagents.
• Initiators trigger initiation of the chain and crease
polymerization rate.
• Initiators are charged chemically in the course of
polymerization.
• Initiators can be decomposed thermally or by irradiation to
produce free radicals.
• Some initiators:

• The initiation of polymerization occurs in two steps:
(2.1)
(2.2)

 Propagation
-Propagation occurs between initiated monomer and thousands
of other monomer molecules with rapid succession to produce
another radicals.
- In propagation, the active center is relocated at the end of the
growing polymer chain.
- Propagation continues until the growing chain radical is
deactivated by chain termination or transfer.

- Derive of ethylene Propagation:
(2.3)
(2.4)
(2.5)

 Termination:
-In termination, the growth activity of a polymer chain radical is
destroyed by reaction with another free radical in system to
produce polymer molecules.
- The termination reactions in polymer production are
combination and disproportionation.
- In termination by combination, two growing polymer chains
react with mutual destruction of growth activity (Equation 2.7).
- Disproportionation a labile atom (usually hydrogen) is
transferred from one polymer radical to another (Equation 2.8).
- The initiator is attached to the resulting polymer molecule.

(2.6)
Combination:
Dispropotionation: (2.7)
(2.8)
-Disproportionation requires energy for breaking of chemical bond at
high reaction temperatures.
- Combination of growing polymer radicals predominates at low
temperatures.
 Chain Transfer:
(2.9)
Chain Transfer may be occur between growing polymer chain

with a solvent, a polymer, a monomer, an initiator or an impurity
molecule.

- Chain Transfer to solvent:
(2.10)
- Chain Transfer to monomer:
(2.11)

Signification of chain transfer:

- A material deliberately added to the system to control
molecular weight by chain transfer is called a chain transfer
agent.
- A substance that if added to the monomer, reacts with chain
radicals to produce either nonradical products or radicals with
such low reactivity as to be incapable of adding monomer is
called a retarder.
- If a retarder is so effective as to completely suppress the rate
and degree of polymerization, it is referred to as an inhibitor.
- Inhibitor is added the system to ensure no polymerization take
place.
Figure 2.1. The influence of retarder and inhibitor on conversion

2.2.2. Steady-State Kinetic of Free-Radical polymerization

• Initiation
The decomposition of the initiator into primary radicals:
(2.12)
The addition of a monomer to the primary radical:
(2.13)
Decomposition of each initiator molecule produces a pair of free
radicals, either or both of which can initiate polymerization.
The rate expression for initiation may be written as:
(2.14)

-Sometime, some of the initiators are decomposited into initiator

radicals, this radicals may react with another radicals
(secondary reaction) to product stable molecules (no initiate for
polymerization). Therefore only a fraction of the initial initiator
concentration is effective in the polymerization process. So,
Capacity of initiators are determined by a factor, called
efficiency factor (f ).
Example: Decomposition of benzoyl peroxide
(C6H5COO)2 2 C6H5COO

- Benzoyl radical can decomposited into phenyl radical:
C6H5COO C6H5 + CO2

Both of radicals initiate for polymerization, we can write:
Initial rate = 2Ri = 2kd [C6H5COO)2]
Phenyl radical can react with each other:
Diphenyl molecule

If both of radicals initiate for polymerization, then f = 1, this

mean that 100% radicals initiate for polymerization.
k1
C6H5COO C6H5 + CO2
k2
C6H5COO + M C6H5COOM
k3
C6H5 + M C6H5M
Therefore, polymer products contain both of groups –C6H5COO

and –C6H5.

In other example: initiator azobisisobutyronitrile (AIBN) is

decomposited, following equation as:
CH3 CH3 CH3

CH3 - C - N= N- C - CH3 2CH3 - C + N2
CN CN CN
But, f = 0.6 because 40% initiator radicals attend in secondary

reaction, as:
CH3 CH3 CH3 CH3
CH3 - C + CH3 - C CH3 - C - N= N- C - CH3
CN CN CN CN
CH3 CH3 CH3

or 2CH3 - C CH3 - CH + CH = CH2
CN CN CN
• Propagation:
(2.15)
In general:
(2.16)
The rate expression of polymerization rate can be written as:
(2.17)
Where

• Termination:
Combination: (2.18)
Disproportionation: (2.19)
If there is no need to distinguish between the two types of

termination, which in any case are kinetically equivalent, then
termination may be respectively as:
(2.20)
Where kt = (ktc+ ktd), ktc, ktd are the rate constants for overall
termination process, termination by combination, termination by
disproportionation.

The termination rate is given by:
(2.21)
At steady state: the total radical concentration remains constant.

This means that, the radicals are being produced and destroyed
at equal rates (Ri = Rt). It follows from Equation (2.14) and (2.21)
that:
(2.22)
The overall polymerization rate is essentially the rate of monomer

consumption during propagation. Substitution of equation (2.17)
and (2.22):
(2.23)

Figure 2.2. Relationship

between initiator concentration
and polymerization rate for
different initiators: A- Benzoyl
peroxide, B- acetyl peroxide in
dimethylphthalate, C- myristoyl
peroxide

2.2.3. The kinetic chain length
The kinetic chain length, , is defined as the average number

of monomers consumed by each primary radical.
• The kinetic chain length depend on the rate of the

propagation relative to the termination rate.
(2.24)
• At the steady state: the rate of initiation equals the rate of

termination, equation (2.24) can be also written as:
(2.25)

• It follows on substitution for Rp and Rt from equation (2.17)

and (2.21), respective that:
(2.26)
• Substitution for [M.] from equation (2.17) yields
(2.27)
• For reactions initiated by the decomposition of an initiator,
From (2.22), we have:
(2.28)

 Determine number average degree of polymerization:

The kinetic chain length should be relative to the number-
average degree of polymerization (Xn ). The degree depend on
chain transfer reactions.
• The first case: There are no chain transfer reactions, by

definition:
(2.29)
Where: Mo = initial number of molecules of monomer present

Mt = number of monomer molecules at time t
Pt = number of polymer molecules at time t

• On differentiating with respect to time, we obtain:

(2.30)
• For a short interval, the instantaneous number-average

degree of polymerization Xn is constant, hence the above
expression becomes:
(2.31)
• For termination by combination: dP(t)/dt = 1/2Rt
• For termination by disproportionation: dP(t)/dt = Rt

• At steady state: Rt = Ri :
For termination by combination (2.32)
For termination by disproportionation (2.33)
• The kinetic chain length is given by equation (2.25), hence:

For termination by combination (2.34)
For termination by disproportionation (2.35)

• The second case: In the presence of transfer reaction of the

kinetic chain length has to be modified to include all possible
sources of polymer molecules. Thus:
(2.36)
• assuming all transfer species:

(2.37)
Where ktr.M, ktr.S, ktr.I : velocity constants for chain transfer to

monomer M, solvent S, and initiator I.
• To estimate the tendency for transfer quantitatively, we define
transfer constants: (2.38)

• Since and Substituting for [I] and [M], equation (2.37) becomes:
(2.39)
(2.40)
• For bulk polymerization (polymerization in absence of a

solvent): Transfer to monomer, equation (2.40) reduces to:
(2.41)

•Transfer to solvent, equation (2.40) reduces to:

(2.42)
Where 1/Xno combines the terms for normal polymerization with transfer to
monomer and represent the reciprocal of the degree of polymerization in the
absence of a solvent.
Table 2.1. Transfer Constants to solvents for the Peroxide Initiation of
Monomer polymerization at 60o C
Transfer Constant, CS x 104
Solvent Methyl Methacrylate Styrene Vinyl Acetate
Acetone 0.195 4.1 25.6 (70o C)

Benzene 0.83 0.028 2.4
Carbon tetrachlorine 2.40 87.0 2023.0 (70o C)
Chloroform 1.77 3.4 554.0 (70o C)
Toluene 0.202 0.105 2075
2.2.4. Temperature dependence of rate and degree of

polymerization
The dependence of the polymerization rate and the number-
average degree of polymerization on temperature can be
demonstrated if the respective relation is expressed in the form
of the Arrhenius equation.
E
dlnk E or  (2.43)
=
dT RT 2 k = A.e RT
Where: k is rate constant for a particular elementary reaction

A is its frequency factor
E is its activation energy
R is gas contant

If we neglect the temperature dependence of f, from Equation

(2.23), we have:
Et Ed
E E -(E p -  )/RT
(-E p + t - d )/RT
k = A.e 2 2 Or k = A.e 2 2
(2.44)
(2.44)
From equation (2.28), we have:
(2.45)

For radical polymerizations, the activation energy of

decomposition (Ed ) is the biggest, around 30 kcal/mol, while Ep
is 5-7 kcal/mol, Et = 3-5 kcal/mol. Thus the temperature
coefficients are
dRp /dT > 0 (2.46)
dXn /dT < 0 (2.47)
These results predict that the rate of polymerization increases

with increasing temperature while the moleccular weight
decreases.

2.3 IONIC POLYMERIZATION CHAPTER 2
2.3.1 Concepts
Ionic polymerizations are heterogeneous chain polymerizations,

involving usually solid inorganic catalysts have capability
decomposite into ion pair and organic monomers
• Ionic polymerizations are characterized by extremely

high reaction rates.
• Ionic polymerizations produce high molecular weight,
stable, uniform polymers.

2.3 IONIC POLYMERIZATION CHAPTER 2
2.3.2 Mechanism of Cationic polymerization
Cationic polymerizations involve formation an ion pair from

catalysts and through the transfer an ion or electron to the
monomer to form carbocation.
• Typical catalysts that are effective for cationic polymerizations

include: AlCl3, AlBr3, BF3, TiCl4, SnCl4. These compounds are
Lewis acids with strong electron-acceptor capability and
sometimes H2SO4.
• To be effective, these catalysts generally require the presence of
a Lewis base such as water, alcohol or acetic acid as a cocatalyst.

CHAPTER 2
 Mechanism: We consider cationic polymerization of
isobutylene
• Initiation:
- First, the catalyst and cocatalyst form a complex:
(2.48)
- The complex donates a proton to an isobutylene molecule to

form a carbocation
(2.49)

CHAPTER 2
• Propagation:
- The carbocation reacts with an isobutylene molecule:
(2.50)
- In general, the propagation reaction can be written as:
(2.51)

CHAPTER 2
• Termination:Termination occurs either by rearrangement of the
ion pair to yield a polymer molecule with an unsaturated terminal
unit and the orginal complex:
(2.52)
or through transfer to a monomer:
(2.53)
-The catalyst is not attached to the polymer molecule.
- Many polymer molecules can be produced by each catalyst
molecule.
CHAPTER 2
 Kinetic
Expression the kinetic of generalized cationic polymerization, let A
the catalyst and RH the cocatalyst, M the monomer, and the
catalyst- cocatalyst complex H+AR-.
Then individual reaction steps can be represented as follows:
(2.54)

CHAPTER 2
- The rate of initiation Ri is given by:

Ri = ki[H+AR-][M] = kiK[A][RH][M] (2.55)
- If the complex H+ AR- is readily converted in the second step of

Equation (2.54) is the rate limiting step, then the rate of initiation is
independent of the monomer concentration. Since AR- remains in
the close vicinity of the growing center, the termination step is first
order: Rt = kt[M+] (2.56)
Where [M+ ] is the concentration of all the chain carriers [HMn+AR-].
The reaction of the terminating agent AR- in the vicinity of the chain
carrier is responsible for the primary difference between the kinetics
of cationic polymerization and that of free-radical polymerization.

CHAPTER 2
- At steady state: Ri = Rt
(2.57)
- Overall rate of polymerization, Rp is given by:

(2.58)
- The number average degree of polymerization:

(2.59)
- If chain transfer dominates, then:
(2.60)

CHAPTER 2
2.3.2. Mechanism of Anionic polymerization
Anionic polymerizations take place with monomers with
electronegative and through pulling electrons from the double
bond and consiquently renders the monomer susceptible to
attack by an electron donor to form carbanion.
• Typical electron- withdrawing substituents that permit the anionic

polymerization of a monomer include: -CN, -COOR, -C6H5, and
–CH=CH2…
• Catalysts for anionic polymerization include Grignard reagent,
organosodium compounds, alkali metal amides, alkoxide, and
hydroxide.

CHAPTER 2
 Mechanism:
• Initiation: may occur in two ways:
(2.61)
(2.62)
Where X, Y are either electron – withdrawing groups or unsaturated groups

capable of resonance stabilization of the negative charge.
M+ is an alkali metal ion.
M+B- may be a metal amide, alkoxide, alkyl, aryl, and hydroxide depending
on the nature of the monomer.
CHAPTER 2
- Pair of anion radicals combine to form a dianion:
(2.63)
- Anionic do not exhibit termination reactions, so systems are

reffered to as living polymers.

CHAPTER 2
• Termination: Because of the reactivity of carbanions with

oxygen, carbon dioxide, and protonic compounds, termination
occurs according to equation (2.64):
(a)
(b)
(2.64)
(c)
(d)
(e)

CHAPTER 2
 Kinetics: The data for the polymerization of styrene by

potassium amide in liquid ammonia support the following steps in
the mechanism of anionic polymerization:
(2.65)

CHAPTER 2
• Steady state kinetics:

(2.66)
(2.67)
From Equations (2.65):
(2.68)
- The Rate of polymerization becomes:
(2.69)

CHAPTER 2
2.4. Coordination polymerization

Coordination polymerization is reaction with presence of
catalysts to form polymers with stereoregular structures.
• Catalysts are reffered as Ziegler- Natta catalyst to coordination

polymerization.
• The components of Ziegler- Natta catalysts are some light
elements of groups I-III in predict table (e.g. Li, Be, Mg, Al)
present as organometalic compounds and halides, or other
derivatives of transition metals of groups IV – VIII (e.g. Ti, V, Cr,
Mo, Rh, Rn, Co).

CHAPTER 2
 Mechanism:
• Initiation:
C2H5)3TiCl3 + (C2H5)2AlCl
(I)
TiCl4 + (C2H5)3Al C2H5
Cl Cl (2.72)
Al
Ti
C2H5
Cl CH2
CH3
(II)

CHAPTER 2
• Propagation: The proposed propagation mechanisms for both
of the monometallic catalyst and bimetallic catalyst are shown
below:
(2.73)
77
Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147
CHAPTER 2
(2.74)

CHAPTER 2
 Kinetic of coordination polymerization
The mechanism of the reaction is described by chemisorption

of monomer molecule on the active site.
2.75
Where Cp* is the number of growing chains on the catalyst

surface
A is the fraction of the surface covered by chemisorbed alkyl
The rate of polymerization is given by:
2.76

CHAPTER 2
Where ks is the insertion rate constant

M is the fraction of the surface covered by chemisorbed
monomer
Uncovered fraction of the active surface is:
(2.77)
Chemisorption of monomer and metal alkyl can expressed:
Where S represent a surface site

CHAPTER 2
(2.78)
(2.79)
(2.80)
(2.81)
[Ms] and [As] are the concentrations of monomer and alkyl at

the surface

CHAPTER 2
At the steady-state: The rates of adsorption and desorption of

monomer and alkyl are equal. And the concentrations of both
monomer and alkyl at steady- state:
(2.82) (2.83)
Where KM = kM+1 /kM-1 and KA = kA+1 /kA-1 are the equilibrium

constants for monomer and alkyl adsorption on the catalyst.
Substitution of (2.82) and (2.83) into equation (2.76), we have:
(2.84)

CHAPTER 2
When the catalyst surface is very large,

then KA[As] and KM[Ms] << 1 and can ignore in the equation (2.84)
So the equation (2.84) can rewriten:
(2.85)
Where kp = ks.KM is a propagation rate constant

C* = C*p0 is the number of active growing chains
and (2.86)

CHAPTER 2
In practice, catalyst activity usually drops with time.

Deactivation of catalyst can decribed:
(2.87)
n=2 seems to be the most popular

CHAPTER 2
2.5. Ring open polymerization (polyme hóa mở vòng)

Ring- open polymerization involves initial ring opening of the
cyclic monomer by the followed by polyaddition. The resulting
polymers are linear
• Applycation of ring- open polymerization:

- In coating
- To produce Fibers
- To produce Elastomers
- To produce adhesives
- To produce thermoplastics

CHAPTER 2
(2.74)
80
CHAPTER 2

CHAPTER 2
CH2 - CH2
8) n - CH2 - CH2 - CH2 - CH2O-
CH2 CH2 n
O
Tetrahydrofuran
CH2
9) n/3 O O - CH2O-
n
CH2 CH2
O
Trioxan
82
CHAPTER 2
Ring open polymerization can be expressed:
nR A (- R - A -)n
Where R is hydrocarbon group, A may be a heteroatom such as

O, S or, a group like amine –NH-, ester –COO-, carboxyl –COOH
.
• Ring open polymerization take place under present a active
substant such as water, acids, amine, alkali.
• Product is linear polymer molecules.

CHAPTER 2
 Mechanism of Ring open polymerization
Consider ring open polymerization of Caprolactam molecules
• Initiation: activation a caprolactam molecule by water to
produce a amino acid molecule
NH
(CH2)5 + HOH H2N-(CH2)5 -COOH
CO
• Propagation: The amino acid attack caprolactam molecule to

ring open
O NH
NH2(CH2)5 - C +
(CH2)5 HOOC-(CH2)5NHCO(CH2)5NH2
OH O=C

CHAPTER 2
And then:
NH
(CH2)5 + HO-[OC(CH2)5NH-] n-1H HO-[OC(CH2)5NH] n-H
CO
General reaction:
NH
n(CH2)5 + H2O H-[NHCH2)5CO] n-OH
CO
Ring open polymerization only stop when obtained balance state.

CHAPTER 2
2.6. Copolymerization
Copolymerization reactions may involve two or more monomers

to form polymers (copolymers).
-Compositions of copolymers may vary from only a small

percentage of one component to comparable proportions of both
monomers.
- Copolymerization permits the production of product polymers
with vastly different properties for a variety of end uses.
- The products of copolymerization can be side chain polymers,
cross-link polymers.

CHAPTER 2
Copolymerization equation:
Some observations are relevant to the consideration of

copolymerization kinetics are:
• The number of reactions involved in copolymerization of two or
more monomers increases with the number of monomers.
Consequently, the propagation step in the copolymerization of two
monomers involves four reactions.
• There are two radicals in the copolymerization of two monomers.
Consequently, three termination steps need to be considered.

CHAPTER 2
• The number of radicals to be considered equals the

number of monomers. Only the terminal of monomer unit in
a growing chain has activity; the nature of the preceding
monomers has no significant influence on the reaction path.
• The composition and structure of the resulting copolymer
are determined by the relative rates of the different chain
propagation reactions.

CHAPTER 2
 Mechanism
By designating the two monomers as M1 and M2 and their
corresponding chain radicals as M1 and M2 , the four
propagation reactions and the associated rate equations in the
copolymerization of two monomers may be written as follows:
(2.75)

CHAPTER 2
-At steady state:

+ The concentrations of M1 and M2 remain constant.
+ The rate of generation and comsumption of these radicals are
equal.
The rate of conversation of M1 and M2 necessarily equals that of
conversion of M1 and M2. Thus from Equation (2.75):
(2.76)
-The rate of disappearance of monomers M1, M2 are given by:
(2.77)
(2.78)

CHAPTER 2
- By dividing Equation (2.77) by equation (2.78) and using
equation (2.76), one of the radicals can be eliminated:
(2.79)
Where r1, r2 are monomer reactivity ratios defined by:
(2.80)
Let F1, F2 are represent the mole fractions of monomers M1, M2 in the
increment of polymer formed at any instant during the polymerization
process, then:
(2.81)
Representing the mole fractios of unreacted M1, M2 in the monomer feed
by f1 and f2 :
(2.82)

CHAPTER 2
- Substitution of Equations (2.81) and (2.82) in (2.79) yields:
(2.83)
 Significance of reactivity ratios:

We have:
(2.84)
A. Ideal copolymerization (r1r2 = 1)
(2.85)
In this case, the copolymer equation reduces to:

or (2.86)

CHAPTER 2
- Case 1: r1 > 1 and r2 < 1 or r1 < 1 and r2 > 1: one of the

monomers is more reactive than the other toward the propagating
species. Consequently, the copolymer will contain a greater
proportion of the more reactive monomer in the random sequence
of monomer units.
- Case 2: r1 = r2 = 1: the composition of the copolymer is the
same as that of the feed and the monomers are arranged
randomly along the chain. The copolymer equation becomes:
(2.87)

CHAPTER 2
B. Alternating copolymerization (r1 = r2 = 0)

When r1 = r2 = 0 (or r1 r2 = 0), each radical reacts exclusively with
the other monomer, that is neither radical can generate itself.
Consequently, the monomer units are arranged alternately along
the chain irrespective of the feed composition. In the case the
copolymer reduces to:
(2.88)
-polymerization continues until one of the monomers is used up

and the stops.
- Producing polymers contain both of monomers with amounts
from a wider range of feed compositions.
CHAPTER 2
C. Block copolymerization (r1 >1, r2 > 1)

If r1 >1 and r2 > 1, then each radical would prefer adding its own
monomer. The addition of the same type of monomer would
continue succesively until there is a chance addition of the other
type of monomer and the sequence of this monomer is added
repeatedly. Thus resulting polymer is a block copolymer.
- Case r1 = r2 =  and r1 r2 > 1: there are no known case of this

type of polymerization.
- Case r1 < 1, r2 < 1: This is an azeotrope. At the azeotrope:
(2.89)
- Practically, the product r1 r2 is almost always less than unity.

Table 2.1. Reactivity ratios of some monomers
Monomer 1 Monomer 2 r1 r2 T(o C)
Acrylonitrile 1,3-butadiene 0.02 0.30 40
Methyl methacrylate 0.15 1.22 80
Styrene 0.04 0.40 60
Vinyl acetate 4.2 0.05 50
Vinyl Chloride 2.7 0.04 60
1,3-butadiene Methyl methacrylate 0.75 0.25 90
Styrene 1.35 0.58 50
Vinyl Chloride 8.8 0.035 50
Methyl methacrylate Styrene 0.46 0.52 60
Vinyl acetate 20 0.015 60
Vinyl Chloride 10 0.1 68
Styrene Vinyl acetate 55 0.01 60
Vinyl Chloride 17 0.02 60
Vinyl acetate Vinyl Chloride 0.23 1.68 60
96
CHAPTER 2
 Polymer composition variation with feed conversion

CHAPTER 2
- For azeotropic copolymerization the solution to equation (2.79)

with d[M1]/d[M2] = [M1]/[M2] gives a critical composition:
(2.90)
(2.91)
-If both r1 and r2 are greater than unity or both are less than unity
then (f1)c lies within accepable range 0 < f1 < 1.
- If r1 > 1 and r2 < 1 or r1 < 1 and r2 > 1 then there will be no
critical feed composition (f1)c.
- When r1 >> 1 and r2 << 1 or r1 << 1 and r2 >> 1 the two
monomers have a tendency to polymerize consecutively.
CHAPTER 2
- Consider a system that is composed initially of M total moles of

the two monomers (M = M1 + M2) and in which the resulting
copolymer is richer in M1 than the feed (F1 > f1). When dM moles
have been polymerized, the polymer will contain F1 d[M] moles of
M1 while the feed content of M1 will be reduced to (M - dM)(f1 - df1)
moles. Writing a material balance for M1:
(2.92)
(2.93)
(2.94)
Where Mo and f1o are the initial values of M and f1.

CHAPTER 2
r1  1 and r2  1
(2.95)
Where the superscripts are given by:

(2.96)
(2.97)
(2.98)

CHAPTER 2
 The factors effect to radical copolymerization reactions

• Monomer reactivity
• Radical reactivity
• Steric effects

Chapter 2 - EMS147

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Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 27

Chain reaction polymerization may be classified as free radical,

• In free radical polymerization, growing chain carriers free radical.

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 28

2.2.1. Free radical mechanism of addition polymerization

Chain-reaction polymerization is the addition of unsaturated

• The growing polymer in chain-reaction polymerization is a free

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 29

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 31

• The initiation of polymerization occurs in two steps:

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 32

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 33

- Derive of ethylene Propagation:

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 34

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 35

Chain Transfer may be occur between growing polymer chain

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 37

- Chain Transfer to solvent:

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 38

Signification of chain transfer:

Figure 2.1. The influence of retarder and inhibitor on conversion

Nguyen.T.Linh, Principles of Polymer Materials Science- EMS 147 40

2.2.2. Steady-State Kinetic of Free-Radical polymerization

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-Sometime, some of the initiators are decomposited into initiator

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- Benzoyl radical can decomposited into phenyl radical:

C6H5COO C6H5 + CO2

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If both of radicals initiate for polymerization, then f = 1, this

Therefore, polymer products contain both of groups –C6H5COO

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In other example: initiator azobisisobutyronitrile (AIBN) is

CH3 CH3 CH3

But, f = 0.6 because 40% initiator radicals attend in secondary

CH3 CH3 CH3

The rate expression of polymerization rate can be written as:

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If there is no need to distinguish between the two types of

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The termination rate is given by:

At steady state: the total radical concentration remains constant.

The overall polymerization rate is essentially the rate of monomer

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Figure 2.2. Relationship

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2.2.3. The kinetic chain length

The kinetic chain length, , is defined as the average number

• The kinetic chain length depend on the rate of the

• At the steady state: the rate of initiation equals the rate of

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• It follows on substitution for Rp and Rt from equation (2.17)

• Substitution for [M.] from equation (2.17) yields

• For reactions initiated by the decomposition of an initiator,

From (2.22), we have:

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 Determine number average degree of polymerization:

• The first case: There are no chain transfer reactions, by

Where: Mo = initial number of molecules of monomer present

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• On differentiating with respect to time, we obtain:

• For a short interval, the instantaneous number-average