Classification of Polymers

1. Based on Origin (Source)

2. Based on Nature of Backbone Chain

Organic Polymers: macromolecule main chain backbone composed of hydrocarbon
(carbon and hydrogen) atom
atoms.

Inorganic Polymers: macromolecule main chain backbone compo

composed
sed of inorganic
elements atoms.

3. Based on Monomer
Homopolymers: Made from one type of monomer that participate and react together in
polymerization reaction.
Copolymers: Made from two or more type of monomers that participate and react
together in polymerization
rization reaction.

1
4. Based on Structure

5. Based on Molecular Chain Orientation (Geometric Rearrangement)

Amorphous Polymers Crystalline Polymers

6. Based on Heat Response

2
Thermosets are resins that undergo reaction during processing to become permanently insoluble
and infusible due to they formed three-dimensional cross linked network structure when heat is
applied.

Characteristics of thermosetting resins:

1. During the hardening the cross-links are formed between adjacent molecules, resulting in
a complex, interconnected network that can be related to its viscosity and performance

2. These cross-links prevent slippage of individual chains, thus preventing plastic flow
under addition of heat

3. If excessive heat is added after cross links, degradation rather than melting will occur.

Ex: Phenolic Resin, Epoxy Resin, Polyester resin

7. Based on Tacticity

The head to tail configuration in which the functional groups are all on the same side of the
chain, is called ‘isotactic polymers’.

3
 If the arrangements of functional groups are at random around the main, it is called ‘atactic
polymers’ e.g. polypropylene.

If the arrangements of side groups is in alternating fashion, it is called ‘synditactic polymers’.

Where R = Alkyl Group

8. Based on Product Applications

9. Based on Polymerization

10. Based on Composition Backbone Chain

Properties of polymer depends on:

1. Degree of Polymerization

2. Molecular Weight of the Polymer

3. Molecular Weight Distribution

4. Glass Transition Temperature

5. Percentage of Crystallinity

4
 6. Structure and
nd Distribution of Chain Branching

Polymer

The term polymer stems from the Greek roots poly (many) and mers (part). The word thus means
"many parts" and designates a molecule made up by the repetition of some simpler unit called a
mer. Polymers contain thousands
housands to millions of atoms in a molecule that is large; they are also
called macromolecules. Polymers are prepared by joining a large number of small molecules
called monomers. The structure of polystyrene, for example, can be written as

Repeating Unit

The fundamental recurring unit of a polymer

polymer.

The mer or repeating unit of the molecule within parentheses with a subscript, such as n, to
represent the number of repeating units in the polymer molecule.

5
Degree of Polymerization (DP or Xn)

This term refers to the number of repeating units in the polymer molecule. We shall use the
abbreviation DP for the degree of polymerization defined in this way. The subscript n used on
the parentheses in the foregoing structural formulas for polymers, represent this DP. The relation
between degree of polymerization and molecular weight M of the same macromolecule is given
by

M = (DP)*Mo

where Mo is the formula weight of the repeating unit.

Oligomer

A molecule consisting of reaction of several repeat units of a monomer but not large enough to
be consider a polymer.

Accordingly, the lower-molecular-weight products with relatively small number of repeating

units in the molecular structure should preferably be called oligomers (Greek: oligo = few) to
distinguish them from polymers. Generally speaking, a species will be called polymeric if

6
articles made from it have significant mechanical strength and oligomeric if such articles are not
strong enough to be practically useful.

Monomer

Monomers are generally simple organic molecules containing a double bond or a minimum of
two active functional groups. The presence of the double bond or active functional groups acts as
the driving force to add one monomer molecule upon the other (of the same or different type) to
make a polymer molecule by a process known as polymerization. As a consequence, the
structure of the repeating unit of a polymer is essentially that or closely related to that of the
monomer molecule(s) from which the polymer molecule is made.

Polymerization

The process by which, monomer combine to form polymers is known as polymerization.

Addition Polymerization

When molecules just add on to form the polymer, the process is called ‘addition polymerization.
In ‘addition polymerisation’ the molecular weight of the polymer is roughly equal, to that of all
the molecules, which combine to form the polymer. Ex; Polyethylene, polypropylene etc.

Condensation Polymerization

When, however, molecules do not just add on but also undergo some reaction in forming the
polymer, the process is called ‘condensation polymerisation’. The molecular weight of polymer
is lesser by the weight of simple molecules eliminated during the condensation process. The
condensation takes place between the two reactive functional groups, like the carbonyl group (of
an acid) and hydroxyl group (of an alcohol) to form polyesters. Ex. Nylon, PET etc.

7
8
Chemistry of Polymerization

Polymerization and Functionality

The process of transformation of monomer molecules to a polymer molecule is known as

polymerization. It is a chemical reaction in which the product molecules are able to grow
indefinitely in size so long as reactants are supplied and suitable conditions exist. Polymerization
may occur if the monomers involved in the reaction have the proper functionalities. Functionality
is a very useful concept in polymer science. The functionality of a molecule is the number of
sites available for bonding to other molecules under the specific conditions of polymerization
reaction. A bifunctional monomer, i.e., a monomer with functionality 2, can link to two other
molecules under appropriate conditions. Styrene, C 6H5CH=CH2, for example, has functionality 2
because of the presence of a carbon-carbon double bond. Since every new linkage consumes two
bonding sites, the product formed when a styrene molecule bonds to another styrene molecule
will still have 2+2-2 or 2 bonding sites and so can continue to add in the same way other styrene
molecules in an addition or chain polymerization reaction leading to the formation of a long-
chain macromolecule. The minimum functionality required for polymerization to take place is 2.
Note that the usage of the term "functionality" here is not the same as in organic chemistry where
a carbon-carbon double bond, for example, is classified as a single functional group. A
polyfunctional monomer is one that can react with more than two other molecules under the
conditions of the polymerization reaction. Examples are divinyl benzene:

9
which is tetrafunctional in reactions involving additions across carbon-carbon double bonds, and
glycerol

which is trifunctional or pentaerythritol, C(CH 2OH)4, which is tetrafunctional in esterifications or

other reactions of alcohols. Functionality in polymerization is, however, defined only for a given
reaction. Thus, a glycol, HOROH, has a functionality of 2 in esterification or ether-forming
reactions, but its functionality is zero in amide forming reactions.

10
Addition Polymerization (Radical Chain Growth Polymerization)

1. The monomers contain at least a double bond that participates in the polymerization
reaction.

2. The initiators for chain polymerization may be different depending upon the nature of
initiation i.e. free radical, cation and anion.

3. The carbon-carbon double bond in vinyl monomers and the carbon-oxygen double bond
in aldehydes and ketones are the two main types of linkages that undergo chain
polymerization.

4. Important characteristics of chain polymerisation.

5. Once the initiation occurs, the polymer chains form very quickly i.e. in the time scale of
10-1 to 10-6 s.

11
 6. The catalyst concentration needed is very low and that means during the course of
polymerisation only monomers and polymers are present.

7. The process is exothermic.

8. High polymers with molecular weights of 10,000 to 10 million can be obtained).

It involves three fundamental steps: initiation, propagation, and termination. In addition, a fourth
step called chain transfer may be involved.

1. Initiation

Initiation involves the acquisition of an active site by the monomer. This may occur
spontaneously by the absorption of heat, light (ultraviolet), or high-energy irradiation. But most
frequently, initiation of free radical polymerization is brought about by the addition of small
quantities of compounds called initiators. Typical initiators include peroxides, azo compounds,
Lewis acids, and organo-metallic reagents. However, while initiators trigger initiation of the
chain and exert an accelerating influence on polymerization rate, they are not exactly catalysts
since they are changed chemically in the course of polymerization. An initiator is usually a weak
organic compound that can be decomposed thermally or by irradiation to produce free radicals,
which are molecules containing atoms with unpaired electrons. A variety of compounds
decompose when heated to form free radicals. Dialkyl peroxides (ROOR), diacylperoxides
(RCO–O–O–CO–R), hydroperoxides (ROOH), and azo compounds (RN› NR) are typical
organic com pounds that can be decomposed thermally to produce free radicals. Benzoyl
peroxide, azobisisobutyronitrile, and di-t-butylperoxide are commonly used free-radical
initiators.

12
The thermal decomposition of benzoyl peroxide, which takes place between 60 and 90°C,
involves the homolytic cleavage of the O–O bond to yield benzoyl free radicals that may react to
yield phenyl radicals and carbon dioxide. An example of photochemically induced free-radical
formation is the decomposition of azo-bisisobutyronitrile by short-wavelength visible light or
near-ultraviolet radiation at temperatures as low as 0°C, where no thermal initiation occurs. In
free-radical polymerization carried out in aqueous medium, the decomposition of peroxide or
per sulfate is greatly accelerated by the presence of a reducing system. This method of free-
radical initiation is referred to as redox initiation. The initiation resulting from the thermal
decomposition of organic compounds discussed above is appropriate only for polymerizations
carried out at room temperature or higher. The enhanced rate of free-radical formation in redox
reactions permits polymerization at relatively lower temperatures. Typical redox reactions for
emulsion polymerization are shown in equations:

13
Persulfate ion initiator (e.g., from K2S2O8) reacts with a reducing agent such as a bisulfite ion
(e.g., from NaHSO3) to produce radicals for redox initiation. Ferric ion may also be used as a
source of radicals. Other redox reactions involve the use of alkyl hydroxides and a reducing
agent such as ferrous ion.

As indicated earlier, free-radical polymerization of some monomers can be initiated by heating

or exposing the monomers to light or high-energy irradiation such as X-rays, γ-rays, and α-rays.
High-energy irradiation of monomers can be carried out either in bulk or in solution. It is
certainly not as selective as photolytic initiation.

When choosing an initiator for free-radical polymerization, the important parameters that must
be considered are the temperature range to be used for the polymerization and the reactivity of
the radicals formed. The presence of certain promoters and accelerators and the nature of the
monomer often affect the rate of decomposition of initiators. For example, the decomposition of
benzoyl peroxide may be accelerated at room temperature by employing ternary or quaternary
amines. Free-radical initiation processes do not require stringent exclusion of atmospheric
moisture, but can be inhibited by substances such as oxygen. Free radicals are inactivated by
reaction with oxygen to form peroxides or hydroperoxides. For monomers such as styrene and
methylmethacrylate that are susceptible to such inhibition, initiation reactions are carried out in
an oxygen-free atmosphere such as nitrogen. It must be emphasized also that organic peroxides,
when subjected to shock or high temperature, can detonate. Therefore these compounds must be
handled with caution. The initiation of polymerization occurs in two successive steps. The first
step involves the formation of radicals according to the processes discussed above. This may be
represented broadly as:

The second step is the addition of the initiator radical to a vinyl monomer molecule:
14
2. Propagation

During propagation, the initiated monomer described above adds other monomers — usually
thousands of monomer molecules — in rapid succession. This involves the addition of a free
radical to the double bond of a monomer, with regeneration of another radical. The active
center is thus continuously relocated at the end of the growing polymer chain.

(1)

Propagation continues until the growing chain radical is deactivated by chain termination or
transfer as discussed below.

The substituted carbon atom is regarded as the head and the unsubstituted carbon atom the
tail of the vinyl monomer. There are, therefore, three possible ways for the propagation step
to occur: head-to-tail (Equation 1), head-to-head (Equation 2), and tail-to-tail (Equation 3).
A random distribution of these species along the molecular chain might be expected. It is
found, however, that head-to tail linkages in which the substituents occur on alternate
carbon atoms predominate; only occasional interruptions of this arrangement by head-to-head
and tail-to-tail linkages occur. In addition, exclusive head-to-head or tail-to-tail arrangements
of monomers in the chain are now known.

(2)

15
 (3)

3. Termination

In termination, the growth activity of a polymer chain radical is destroyed by reaction with
another free radical in the system to produce polymer molecule(s). Termination can occur by
the reaction of the polymer radical with initiator radicals. This type of termination process is
unproductive and can be controlled by maintaining a low rate for initiation.

The termination reactions that are more important in polymer production are combination (or
coupling) and disproportionation. In termination by combination, two growing polymer
chains react with the mutual destruction of growth activity (Equation 1), while in
disproportionation a labile atom (usually hydrogen) is transferred from one polymer radical
to another (Equation 2)

(1)

(2)

16
 Coupling reactions produce a single polymer, while disproportionation results in two
polymers from the two reacting polymer chain radicals. The predominant termination
reaction depends on the nature of the reacting monomer and the temperature. Since
disproportionation requires energy for breaking of chemical bonds, it should become more
pronounced at high reaction temperatures; combination of growing polymer radicals
predominates at low temperatures.

Chain Transfer

Ideally, free-radical polymerization involves three basic steps: initiation, propagation, and
termination, as discussed above. However, a fourth step, called chain transfer, is usually
involved. In chain-transfer reactions, a growing polymer chain is deactivated or terminated by
transferring its growth activity to a previously inactive species, as illustrated in below equation:

The species, TA, could be a monomer, polymer, solvent molecule, or other molecules
deliberately or inadvertently introduced into the reaction mixture. Depending on its reactivity,
the new radical, A·, may or may not initiate the growth of another polymer chain. If the
reactivity of A· is comparable to that of the propagating chain radical, then a new chain may be
initiated. If its reactivity toward a monomer is less than that of the propagating radical, then the
overall reaction rate is retarded. If A· is unreactive toward the monomer, the entire reaction
could be inhibited. Transfer reactions do not result in the creation or destruction of radicals; at
any instant, the overall number of growing radicals remains unchanged. However, the occurrence
of transfer reactions results in the reduction of the average polymer chain length, and in the case
of transfer to a polymer it may result in branching.

The major effect of' chain transfer to a saturated small molecule (solvent, initiator, or deliberately
added chain-transfer agent) is the formation of additional polymer molecules for each radical
chain initiated. Transfer to polymer and transfer to monomer with subsequent polymerization of
the double bond lead to the formation of' branched molecules. The latter reaction has a
pronounced effect on molecular weight distribution and is important in the production of' graft
copolymers. The efficiency of compounds as chain-transfer agents varies widely with molecular
structure. 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) are the most
general. Example for styrene + butyl mercaptan:

17
The sulfur-centered
centered radical reinitiates very efficie
efficiently.
ly. The result is a decrement of the molecular
weight 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).

Many peroxides used as initiators have significant chain transfer reactions. Dialkyl and diacyl
peroxides undergo chain transfer due to breakage of the O O--O bond. Here is an example of
transfer to initiator featuring acrylonitrile and benzoyl perox
peroxide (BPO):

One chain is terminated, but another one initiates. This particular reaction reduces MW and
wastes initiator (i.e., an initiator molecule is consumed, but no new chains are begun).
Sometimes this process is called induced decomposition of the initiator. It is a common side
reaction for the peroxy initiators, but happens less often with the azo initiators.

In some laboratory polymerizations, the solvent itself acts as the chain transfer agent. Aromatic
hydrocarbons are rather unreactive unless they have benzylic hydrogens. Aliphatic hydrocarbons
become more reactive when substituted with halogens. Carbon tetrachloride and carbon
tetrabromide are quite reactive. The reactivity of various polymer radicals to transfer varies
widely. Transfer reactions
ons offer a valuable means for comparing radical reactivities. For
example, the chain transfer reaction for vinyl polymerization in CCl4 can be represented by:

18
where ktr,S is the rate constant for chain transfer to solvent. Solvents are normally, not used in
industrial free-radical polymerizations, for economic reasons, and the chain transfer agents in
these reactions are ingredients that are added deliberately to limit the molecular weight of the
polymer.

Chain transfer is a chain-breaking reaction; it results in a decrease in the size of the propagating
polymer chain. The effect of chain transfer on the polymerization rate is dependent on whether
the rate of reinitiation is comparable to that of the original propagating radical.

Reinitiation is rapid in cases 1 and 2, and one observes no change in the polymerization rate. The
same number of monomer molecules are consumed per unit time with the formation of larger
numbers of smaller-sized polymer molecules. The relative decrease in Xn depends on the
magnitude of the transfer constant. When the transfer rate constant ktr is much larger than that
for propagation (case 2) the result is a very small-sized polymer (Xn~1–5)—referred to as
telomer. When reinitiation is slow compared to propagation (cases 3 and 4) one observes a
decrease in Rp as well as in Xn. The magnitude of the decrease in Rp is determined by the
relative values of kp and ktr. The remainder of this section will be concerned with case 1. Cases
3 and 4 will be considered further. Case 2 (telomerization) is not within the scope of this text.
For chain transfer by case 1 the kinetic chain length remains unchanged, but the number of
polymer molecules produced per kinetic chain length is altered. The number-average degree of
polymerization is no longer given by n or 2n for disproportionation and coupling, respectively.

Chain transfer is important in that it may alter the molecular weight of the polymer product in an
undesirable manner. On the other hand, controlled chain transfer may be employed to advantage
in the control of molecular weight at a specified level. The degree of polymerization must now
be redefined as the polymerization rate divided by the sum of the rates of all chain-breaking
reactions (i.e., the normal termination mode plus all chain-transfer reactions). For the general
case of a polymerization initiated by the thermal homolysis of a catalyst and involving
termination by a combination of coupling and disproportionation and chain transfer to monomer,
initiator, and the compound S (referred to as a chain-transfer agent), the number average degree
of polymerization follows from Eqn. as:

19
The first term in the denominator denotes termination by a combination of coupling and
disproportionation, and the other terms denote chain transfer by monomer, chain-transfer agent,
and initiator, respectively. Consider now the simpler case when disproportionation does not
occur (a=1). Equation becomes

A chain-transfer constant C for a substance is defined as the ratio of the rate constant ktr for the
chain transfer of a propagating radical with that substance to the rate constant kp for propagation
of the radical. The chain-transfer constants for monomer, chain-transfer agent, and initiator are
then given by:

Combining all eqns. and with Ri= Rt yields

which show the quantitative effect of the various transfer reactions on the number-average
degree of polymerization. Various methods can be employed to determine the values of the
chain-transfer constants. This equation is often called the Mayo equation.

20
Inhibition and Retardation

 A retarder is defined as a substance that can react with a radical to form products
incapable of adding monomer.

 It reduces the concentration of radicals.

 In the simplest case, the retarder may be a free radical, such as triphenylmethyl, which is
too unreactive to initiate a polymer chain.

 The mechanism of retardation is simply the combination or disproportionation of

radicals.

 Molecular oxygen presents peculiar behavior toward free radical polymerization.

 O2 is a very potent inhibitor for most common vinyl monomers. Polymerization media
are usually thoroughly purged with inert gas to remove O2, otherwise the reaction may
not work.

 Traces of O2 can initiate free radical vinyl polymerization (indirectly). O2 can react with
some monomers or with trace impurities to form peroxy compounds that are thermal
initiators.

The addition of certain substances suppresses the polymerization of monomers. These substances
act by reacting with the initiating and propagating radicals and converting them to either non-
radical species or radicals of reactivity too low to undergo propagation. Such polymerization
suppressors are classified according to their effectiveness. Inhibitors stop every radical, and
polymerization is completely halted until they are consumed. Retarders are less efficient and stop
only a portion of the radicals. In this case, polymerization occurs, but at a slower rate and lower
polymer molecular weight. The difference between inhibitors and retarders is simply one of
degree and not kind. Inhibition and retardation are usually the cause of the irreproducible
polymerization rates observed with insufficiently purified monomers. Impurities present in the
monomer may act as inhibitors or retarders. On the other hand, inhibitors are invariably added to
commercial monomers to prevent premature thermal polymerization during storage and
shipment. These inhibitors are usually removed prior to polymerization or, alternatively, an
appropriate excess of initiator may be used to compensate for their presence.

21
22
True chain-transfer agents lower polymer molecular weights but do not affect polymerization
rates. Retarders and inhibitors lower polymerization rates and polymer molecular weights.
Nevertheless, CS values for retarders and inhibitors give useful practical information.

Types of Inhibitors and Retarders

As with chain-transfer agents, one observes that the inhibition constant for any particular
compound varies considerably depending on the reactivity and polarity of the propagating
radical. Various types of compounds act as inhibitors and retarders. Stable free radicals that are
too stable to initiate polymerization but that can still react with radicals are one type of radical
terminator. Diphenylpicrylhydrazyl (DPPH) is such a radical and its use as a radical scavenger.
The stoichiometry between the number of kinetic chains terminated, and the number of DPPH
radicals consumed is 1:1. The most useful class of inhibitors are molecules that react with chain

23
radicals to yield radicals of low reactivity. Quinones such as benzoquinone and chloranil
(2,3,5,6-tetrachlorobenzoquinone) are an important class of inhibitor.

ACTION OF QUINONES

ACTION OF NITROBENZENE

Aromatic nitro compounds terminate propagating chains, with a greater effect for more reactive
and electron-rich radicals. Nitro compounds inhibit vinyl acetate, retard styrene, but have little
effect on methyl acrylate and methyl methacrylate. The effectiveness increases with the number
of nitro groups on the ring. 1,3,5-Trinitrobenzene has z values that are 1–2 orders of magnitude
greater than nitro benzene. The mechanism of radical termination involves attack on both the
aromatic ring and the nitro group. Attack on the aromatic ring yields radical XXXII, which reacts
with another propagating radical (Eq. 3-149) or with monomer (Eq. 3-150).

Attack on the nitro group leads to radical XXXIII, which can react with other propagating
radicals (Eqs. 3-151 and 3-152) or cleave to nitrosobenzene and Mn O
radical (Eq. 3-153). Both nitrosobenzene and Mn O
can react with and terminate other propagating radicals.

24
The reaction in Eq. 3-152 probably also involves disproportionation—hydrogen atom transfer
from the propagating radical to XXXII. Overall, one observes high y values—up to 5 or 6 for
1,3,5-trinitrobenzene.

Some substances suppress free-radical polymerization of monomers by react ing with primary
radicals or polymer radicals to yield either non-radical products or radicals that are of too low
reactivity to undergo propagation. Such polymerization suppressors are called inhibitors or
retarders depending on their effectiveness. Inhibitors stop every radical and polymerization is
completely halted until they are consumed. Retarders are less efficient and stop only a fraction of
the radicals. In this case, polymerization is not halted but it occurs at a slower rate.

Comparison of conversion-time plots for normal, inhibited, and retarded free-radical

polymerization. Curve 1: normal polymerization; curve 2: inhibition; curve 3: retardation;
curve 4: inhibition followed by retardation.

Polymerization is completely stopped by an inhibitor during an induction or inhibition period

(curve 2). At the end of this period, when the inhibitor has been consumed, polymerization
proceeds at the same rate as in the absence of inhibitor (curve 1). A retarder lowers the
polymerization rate without an inhibition period (curve 3). Some substances exhibit complex
behavior (curve 4). This behavior is not at all uncommon and may be exhibited by a substance
that initially acts as an inhibitor but is converted to a product which acts as a retarder after the
inhibition period. Impurities present in a monomer may act as inhibitors or retarders and those
are usually the cause of the irreproducible polymerization rates observed with insufficiently

25
purified monomers. On the other hand, inhibitors are invariably added to commercial monomers
to prevent premature thermal polymerization during storage and shipment. These inhibitors are
removed prior to polymerization or, alternately, an appropriate excess of initiator may be used to
compensate for their presence. The difference between inhibitors and retarders is simply one of
degree and not kind. Both are either chain transfer agents or act by addition processes to provide
an alternative reaction path to propagating polymer radicals:

If the new radicals A" and M~Q" do not react readily with monomer, there will be a decrease in
the concentration of reactive radicals and a consequent fall in the rate of polymerization. If the
rate of reaction is very much greater than that of reaction the new radicals A" and M,~Q" do not
add monomer then high-molecular weight polymer will not be formed and the rate of
polymerization will be effectively zero. This is a case of inhibition. In retardation the rate of
polymerization is slowed down but not reduced to zero. This occurs (a) if the rate of reaction is
close to that normal propagation reaction and the new radicals A" and M,~Q" not reinitiate (b) if
reactions compared to reaction but the new radicals A" and MnQ" that are formed reinitiate
slowly. Quinones are probably the most important class of inhibitors. The following transfer
reactions may take place in the presence of quinone:

The inhibitor radicals formed in the above reactions are stabilized by resonance to such an extent
that they do not start chains and initiate polymerization. They disappear partly through
disproportionation (forming quinone and hydroquinone):

and partly by combining with each other (dimerization) or with new chain radicals. Reaction
results in the regeneration of one inhibitor molecule per each pair of inhibitor radicals. Therefore
this would lead to a 2:1 stoichiometry between the number of kinetic chains terminated [such as

26
by reaction and the number of quinone molecules consumed. Disappearance of inhibitor radicals
by dimerization would lead to a 1:1 stoichiometric ratio. Hydroquinone and Other
dihydroxybenzenes such as t-butyl catechol also act as inhibitors, but only in the presence of
oxygen. The inhibiting effect is due to their oxidation to quinone. A large number of other
substances are also active inhibitors. These include oxygen, NO (one of the most effective
inhibitors, so much so that some highly reactive monomers can be distilled only under an
atmosphere of NO), aromatic nitro compounds, numerous nitroso compounds, sulfur compounds,
amines, phenols, aldehydes and carbamates. An interesting inhibitor is molecular oxygen. Being
a diradical, oxygen reacts with chain radicals to form the relatively unreactive peroxy radical:

Effects of Temperature and Pressure on Chain Polymerization

Thermochemical and thermodynamic data give valuable insight into the mechanisms of vinyl
polymerization reactions. By the usual Arrhenius treatment, the temperature dependence of
the rates of the various steps in radical chain polymerization can be separated into an energy
of activation representing the amount of energy that the reactant molecules must have to be
able to react on collision, and a frequency factor which allows estimation of the fraction of
the collisions that lead to reaction Enthalpies of polymerization are readily measured and
may also be calculated from bond dissociation energies Differences between the two values
give an indication of the amount of steric hindrance in the polymer Free energies of
polymerization reactions can be calculated for some simple cases an give information on the
thermodynamic equilibria involved in polymerization.

Enthalpies and Free Energies of Polymerization

Enthalpies of Polymerization: These may be obtained from the heats of combustion of

monomer and polymer or directly by a calorimetric experiment; they may also be calculated
from bond dissociation energies When the two results are compared, it is seen that the
observed enthalpy of polymerization is equal to or somewhat lower than the calculated heat
For vinyl compounds with two substituents on the same carbon atom the difference is 3-8
kJ/mole This is attributed to steric repulsion between the substituent groups in the polymer.
For monosubstituted vinyl derivatives the difference is much lower; only for styrene is it
definitely greater than 4 kJ/mole. Enthalpies of polymerization (Table 3-5) vary over a wide
range, reflecting differences in resonance stabilization and conjugation, steric strain in
monomer and polymer, and (if present) dipole interactions and hydrogen bonding.

Entropies and Free Energies of Polymerization: The entropy of polymerization is largely

determined by the loss of the translational entropy of the monomer on polymerization Values
of AS are therefore relatively insensitive to monomer type (Table 3-5) Both ΔH and ΔS are

27
negative, but the exothermic nature of the polymerization reaction outweighs the influence of
the entropy term in so that the free energies are negative at usual temperatures.

At elevated temperatures the entropy term increases, and when ΔH = T ΔS, ΔG = 0 and the
polymerization reaction is in equilibrium with the reverse reaction of' depolymerization. This
temperature is known as the ceiling temperature for the polymer. Some ceiling temperatures
for pure monomers are 61 oC for α-methylstyrene, 220°C, for methyl methacrylate, and
310°C for styrene.

The calculation of' the enthalpies and entropies of' reaction of free radicals has been carried
out for hydrocarbons and fluorocarbons and applied to the synthesis equations for
polyethylene and polytetrafluoroethylene. Values of enthalpy and free energy for the
addition of' monomer to the radical become less negative as the length of the chain radical
increases in the first few propagation steps. After the growing free radical reaches a length of
about eight carbon atoms, all successive steps have the same enthalpy and free energy of'
reaction, the same as those for the overall polymerization step.

Activation Energies and Collision Factors

28
29
30
Autoacceleration (Trommsdorff Effect)

Since the initiator concentration remains fairly unchanged in the course of vinyl polymerization,
if the initiator efficiency is independent of monomer concentration, first-order kinetics with
respect to the monomer is expected. This is indeed observed over a wide extent of reaction for
the polymerization of styrene in toluene solution with benzoyl peroxide as initiator (Figure 7.3).
The polymerization of certain monomers, either undiluted or in concentrated solution, shows a
marked deviation from such first-order kinetics. At a certain stage in the polymerization process,
there is a considerable increase in both the reaction rate and the molecular weight. This
observation is referred to as autoacceleration or gel effect and is illustrated in Figure 7.4 for
polymerization of methyl methacrylate at various concentrations of the monomer in benzene.

Observe that for monomer concentrations of up to 40%, plots show that first-order kinetics is
followed. However, at higher initial monomer concentrations, a sharp increase in rate is observed
at an advanced stage of polymerization. At the same time, high-molecular-weight polymers are
produced. Autoacceleration is particularly pronounced with methyl methacrylate, methyl
acrylate, and acrylic acid. It occurs independent of an initiator and is observed even under
isothermal conditions. In fact, where there is no effective dissipation of heat, autoacceleration
results in a large increase in temperature.

31
To understand the physical phenomena taking place during autoacceleration, let us look more
carefully at the rate equation:

Since autoacceleration is not a function of the initiator, an increase in the factor fk d does not
provide an explanation for the observation. Consequently the phenomenon of autoacceleration
could be due to an increase in the propagation rate constant k p and/or a decrease in the
termination rate constant kt. Trommsdorff attributed autoacceleration to a decrease in the
termination rate. As the concentration of polymer molecules generated builds up, the viscosity of
the medium increases. This reduces the overall diffusion rate of growing radical-bearing polymer
molecules even though the intrinsic reactivity of the radical remains unaffected. As a result, the
bimolecular annihilation of radical reactivity becomes diffusion-controlled. This reduction in
termination rate, in turn, increases the concentration of active radicals, and the rate of local
consumption of monomers increases proportionately. The overall rate of propagation, however,
remains relatively unaffected since the diffusion of monomers is hardly affected by the high
medium viscosity. This reduction in termination rate with little or no change in the propagation
rate leads to a rapid rise in the molecular weight.

A further reference to Figure 7.4 shows that autoacceleration does not result in complete
polymerization of monomers. Also, the higher the dilution, the higher the extent of conversion.
Pure poly(methyl methacrylate) has a glass transition temperature of about 90°C. It therefore
follows that when the percentage of polymers formed reaches a certain high value, the reaction
mixture is transformed into a glass at temperatures below 90°C. Propagation becomes monomer
diffusion-controlled, and there is a virtual cessation of polymerization. There is ample

32
experimental evidence to support the above expla nation for the phenomenon of
autoacceleration.

Gelation

33
Initiator Efficiency (Cage Effect)

Initiators are not used efficiently in free-radical polymerizations. This becomes apparent
when a material balance is performed on the amount of initiator that is decomposed during a
polymerization and compared with the amount that initiates polymerization and thus
becomes a part of the polymer formed.

The values of f for most initiators lie in the range of 0.3-0.8. The major cause of this low f is
wastage of primary radicals in "cage" reactions. When an initiator molecule decomposes
forming primary radicals, the radicals are each other’s nearest neighbors for about 10 -10 s.
During this short interval the primary radicals are surrounded by a "cage" of solvent and
monomer molecules through which they must diffuse to escape each other. While in the cage,
the radicals can be expected to be colliding on the average once every 10 -13 s (the vibrational
frequency of a diatomic molecule at reaction temperatures being approximately 10 13 s-1) and
so any reaction can take place. To illustrate, the decomposition of benzoyl peroxide could
lead to the following reactions:

Equation (6.40) represents the primary step of initiator decomposition into two radicals,
which are held within the solvent cage (with solvent and/or monomer molecules comprising

34
the cage wall). The radicals in the solvent cage may undergo recombination [i.e., reverse of
Eq. (6.40)], reaction with each other [Eq. (6.41)], reaction with a monomer molecule
contained the wall of the cage [Eq. (6.42)], or diffusion out of the solvent cage [Eq. (6.43)].
Once outside the solvent cage, the radicals may react with monomer [Eq. (6.44)] or
decompose according to Eq. (6.45)] to yield a radical which may react with monomer. Once
one or the other radical leaves the cage, it is extremely unlikely that the pair will encounter
each other again.

Recombination of the primary radicals [the reverse of Eq. (6.40)] has no effect on the
initiator efficiency. Initiation of the polymerization occurs by reactions (6.42), (6.44), and
(6.46). The initiator efficiency is decreased by the reaction indicated by Eq. (6.41) since the
reaction products are stable and cannot give rise to radicals. This reaction is usually much
more significant than any other in decreasing the value of f. Since the rate constants for
radical-radical reactions are in the range 107 L/mol-s and higher, and the concentration of
radicals in the solvent cage is high (~10 mol/L), there is a reasonable probability that the
radical pair in the solvent cage will react as indicated by Eq. (6.41). All initiators suffer cage
wastage reactions. For AIBN, for example, f is only 0.6 at 60°C because of these reactions.

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