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Step-growth kinetics

As a result of their macromolecular nature, polymers

would be expected to have retarded mobility.

It was therefore predicted, purely on theoretical

arguments, that the chemical reactivity of polymers
should be low.

Flory states that the intrinsic reactivity of all

functional groups is constant, independent of the
molecular size.

A pair of neighboring functional groups may collide

repeatedly before they either diffuse apart or react. The
lower the diffusion rate, the longer these groups remain in
the same vicinity.

Kinetics of polyesterification

The kinetics of most other common SG polym. follows an analogous

pathway (Carrahers book).
catalyzed systems

Rate of polymerization =



for [A]=[B]







= [][
]

= []


[]  =  integrate=> kt=  

kt=   (p is franction of reacted groups)  = (1 )

kt=

 ()

 => XN=A0kt + 1


XN= A0/At = 1/(1 )

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XN=A0kt + 1

predicts a linear relationship of XN=A0/At with reaction time.

The number-average degree of Polymerization, Xn

If p is the fraction of functional groups that have reacted

,- = -./012 34 /3819.81: 7 7 :195459 5/1 =

Useful high molecular weight linear polymers are not obtained

unless the value for the fractional conversion p is at least
0.990, i.e., a DP greater than 100.

-./012 34 32565-78 /3819.81:

;
;




=



 ()

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Step-Chain growth

C-G Polymerizations
Chain growth polym. is usually rapid.

Unlike the case of SG polym.

Very long macromolecules can be formed just

after induction of the reaction.

A chain reaction usually consist of at least

three steps

Initiation Propagation - Termination.
 they can occur simultaneously.

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A  P*
P* + M  PM*
PM*n + M  PM*(n+1)
PM*n  PMn
PM*n + T  PM + T*
T* + M  TM*

(initiation 1st phase)

(initiation 2nd phase)
(propagation)
(termination)
(chain transfer)

Main Reactions used in C-G Polym.

Free radical: whose propagating active centers

involve free radicals.
Anionic: require nucleophilic reactive centers.
Cationic: whose propagating species are
electrophiles.
Coordination: whose active centers are complexes
formed coordination between monomer molecules
and transition metal atoms.

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The initiator is a radical, and the propagating site of

reactivity (*) is a carbon radical.
Cationic Polymerization The initiator is an acid, and the
propagating site of reactivity (*) is a carbocation.
Anionic Polymerization The initiator is a nucleophile,
and the propagating site of reactivity (*) is a
carbanion.
Coordination Catalytic Polymerization The initiator is a
transition metal complex, and the propagating site of
reactivity (*) is a terminal catalytic complex.

Reactions Compatible with Chain Poly.

Monomers carrying unsaturated groups;

Cyclic strained monomers;

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i.e.

In general, initiation requires energy

And, propagation produces energy.

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When temperature is raised, the entropy term

increases as well until becoming equal to enthalpy
term. -> The polymerization cannot proceed.

The maximum temperature is called ceiling

temperature.

As temperature increases, at some point the entropy

contribution overwhelms the enthalpy contribution.
Above this temperature, depolymerization is faster
than polymerization. The polymer "unzips" back to
monomer.

Free Radical Chain Polymerization

Most of the polymers are prepared by free radical

polymerization.

Free radicals form by homolytic bond cleavage.

A species containing an atom with a single unpaired

electron is called a radical (often free radical).

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Double bonds

the two pairs of electrons which make up the double

bond are not the same.
One pair is held securely on the line between the two
carbon nuclei in a bond called a sigma bond.
The other pair is more loosely held in an orbital above
and below the plane of the molecule known as a pi bond.

Equivalent views of C=C

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The free radical, Ra, uses one of the electrons in

the pi bond to help to form a new bond between
itself and the left hand carbon atom. The other
electron returns to the right hand carbon.
This is energetically worth doing because the new
bond between the radical and the carbon is
stronger than the pi bond which is broken.
You would get more energy out when the new bond
is made than was used to break the old one. The
more energy that is given out, the more stable the
system becomes.

Planar to Tetrahedral

sp2-hybridized carbon atoms are transformed into

sp3 ones.

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Tacticity

This notion is particularly interesting in the case of

vinyl and related polymers.
Chiral Carbon: C atom with 4 different groups.
Enantiomer: is one of two stereoisomers that are mirror
images of each other that are non-superposable.

Enantiomers form different crystals.

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Free Radical Chain Polymerization

Free radicals can be involved in six reactions;

1. Addition
2. Abstraction/transfer
3. Disproportionation
4. Combination

R*+CH2=CRR RCH2C*RR
R*+RX RX+*R
2 RCH2CH2* RCH2CH3+RCH=CH2
R*+*R R-R

5. Fragmentation
6. Rearrangement

RA* R*+A
RRR**RRR

Free radical polymerization kinetics

Initiation:

kc is non-negligible, the proportion really active is

called efficiency (f) of this initiator.

R +M

R +R

kd

ki

kc

2R

.
.

RM

R-R

as side reaction

Ri = 2f kd[I] ; dissociation step is slower, each initiator

forms two radicals.

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Free radical polymerization kinetics

Propagation:

Rp = kp[RM*][M]

Termination: combination or disproportionation

Rt = kt[RM*]2

Free radical polymerization kinetics

Assuming that the number of active chains

remains constant;
Ri=Rt
2f kd[I] = kt[RM*]2
Rp = kp (f [I]kd/kt)1/2[M]
@ A B

<=

Xn=

<>

?= ( B C ) [E]

?C 4[F]

=K

[E]
[F]D/

12

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Some conclusions

The rate of propagation [M] and [I]1/2.

The rate of termination [I].
The av. MW [M] and 1/ [I]1/2.
The first chain is that is initiated rapidly produces
a HMW polymer.
Increasing the temperature increases the
concentration of free radicals and thus rate of
reactions, but it decreases the av. MW.
If the temperature exceeds the ceiling
temperature the polymer will decompose and no
propagation will take place.

Initiation of FR Polymerizations

A. Generation of Initial Free Radicals

Most of the generators are unstable molecules that can

homolytically dissociate under thermal effect, due to their
weak covalent


The electronegativity of the elemets is high.

Ed0-0 < EdN-N < EdC-C



The stabilization (by electron-donor and/or resonance effects) of

the radicals resulting from the dissociation

Molecule
H-CH3
H-CH2-CH3
H-C(CH3)
H-CH2-Ph

Ed
426
393
376
322

Estab.(kJ/mol)
0
33
50
104

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Thermal Initiators

Organic peroxides and hypoperoxides are very

commonly used.
Decomposition of peroxides can be single or multisteps.

Water soluble initiators;

Azo compounds;

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Photochemical initiation

Photochemical initiation;

Ionizing ratiations (,);

AB  +AB. + e-  +A + B.
Both free radicals and radical ions can be formed
upon radiation and initiate polymerization.

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Propagation of FR Polymerizations

Propagation: Generally, is very fast and

corresponds to an exothermic reaction .

Like the initiation step, the reaction mechanism is

of the free-radical-addition type.

The relative reactivities of monomers is influenced

by two factors:

the stability of the monomer toward addition

of a free

radical

the stability of the monomer radical thus formed. (!!)

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steric effects: 1,2-disubstitution and bulky

substituents decrease reactivity in radical
polymerizations.

resonance: Resonance stabilization of the radical

also makes the radical less reactive towards
propagation.

Effect of substituents

Steric hindrance and electronic effects are

involved in the intrinsic reactivity of R*.

The two same effects also determine the reactivity of

the monomer (M).

The proper reactivity of M can be measured by

methyl affinity.

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Unsubstituted (ethylene)
Works fine.
Monosubstituted
Works fine.
1,1-Disubstituted
Usually works.
1,2-Disubstituted
Seldom works.
Trisubstituted and
tetrasubstituted
Almost never works.
Except fluorinated monomers!

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Stabilization of Radicals

Any substituents stabilize the chain end radical.

Inductive (weak)
 Cl, OCH3, OCOCH3

Resonance (strong)
 CO2CH3, CN, phenyl, etc.

The more stable the radical that forms from the

monomer, the lower the polymerization rate
constant and polymerization rate.

Vinyl acetate, a very stable monomer, has a very high

kp (reactive radical forms).

Styrene, is a very reactive monomer, but forms a
stable radical, and so has a lower kp.

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The higher the stabilization of growing radicals, the

lower will be the proportion of irregular (head-tohead) placements.

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Resonance Stabilization of Radicals

Problem with alkyl groups

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Apparently, the resonance effect of the ester

group tips the balance in favor of propagation
versus hydrogen abstraction.

Termination of FR Polymerizations

Implies the collision of two growing free radicals

which is less probable than their collision with
monomer molecules.

They can combine or disproportionate.

They can combine easily when there is no steric

factors.

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Chain Transfer

Radicals are reactive beasts.

Chain transfer occurs when a radical species
reacts with a nonradical species.
In the most common occurence, the chain end
radical attacks a weak bond. An atom gets
transfered to the chain end.

In many cases, a chain transfer agent is added

deliberately to the reaction mixture.
Many compounds work well for this purpose, but
mercaptans (also known as thiols; R-SH) are the
most general.

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The sulfur-centered radical reinitiates very

efficiently.
The result is a dimunition of the MW without
changing the overall rate of conversion of monomer
to polymer.

(Using more initiator is another way to decrease MW,

but the reaction rate would increase proportionally, a

possibly dangerous situation.)

Chain Transfer

Naturally, there are many even-electron species

present in the reaction mixture (i.e., monomer,
initiator, solvents, polymer chains, etc.).

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Chain Transfer to Polymer

If the chain end radical attacks an atom on the backbone of

the same or another chain, the result is a new radical that
can reinitiate to form a branch. This reaction happens very
commonly during the free radical polymerization of
polyethylene.

The chemistry is driven by the greater stability of the

secondary radical that forms, compared to the
primary one at the chain end.
The most convenient site of attack is a hydrogen atom
that is a short distance back on the same chain.
Branches disrupt chain packing, and decrease degree
of crystallinity, creating low density polyethylene
(LDPE). LDPE is much softer than the version that is
linear (made by coordination polymerization).

Chain transfer to polymer occurs to a lesser extent in

many other systems.

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Inhibitors

Consider what happens if chain transfer occurs,

but the new radical is incapable of reinitiation.

If so, this is a kind of termination reaction. The

agent responsible is called an inhibitor. There are
many kinds of inhibitors, but the most common are
phenols with bulky groups ortho to the OH group.

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Autoacceleration

Autoacceleration only occurs during

polymerizations with high concentrations of
monomer (i.e., little or no solvent).

The reaction proceeds normally for a while, then

suddenly the rate of polymerization goes up
dramatically.

The molecular weight of chains that grow during

the accelerated period is substantially higher than
that of chains that grew earlier.

Termination involves the reaction between two chain ends.

However, in concentrated solutions, the viscosity of the
reaction mixture becomes high as polymer chains form.
This high viscosity hinders the diffusion of chains because
of entanglements, so the rate of termination slows
considerably.
However, the diffusion of small molecular monomers is
hardly affected by viscosity, so propagation proceeds as
before.
In addition, initiator continues to add more free radicals to
the system.
Chains grow without termination, so the conversion is rapid
and the MW is high.

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Conventional Radical Polymerization

Broad MWD

Dead Polymer

Controlled Radical Polymerization

T
T

Narrow MWD

T
T

Living Polymer

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