ASSIGNMENT – MAT5002 – PART B (50/100)

QUES 1)
SOL 1.
INITIATION

This step involves the generation of active species. The free radicals can be produced in a
number of ways, including thermal or photochemical decomposition of organic peroxides,
hydroperoxides, azo or diazo compounds. Other methods of free radical generation are high-
energy radiation and oxidation-reduction (redox) reactions.

The two most common initiators (I) are benzoyl peroxide (BPO) and 2,2'-azo-bis-
isobutyrylnitrile (AIBN). Both molecules have a strong tendency to fall apart into two
fragments with unpaired electrons, the so-called free radical initiators:

I → 2 R·

Following its generation, the free radical then reacts with a vinyl monomer, that is, it adds to
one of the electrons of the double bond of the vinyl monomer and the remaining electron
becomes the new free radical:

R· + M → RM·

Thus the process of chain initiation involves two steps; the first being the decomposition of
the initiator (e.g. BPO or AIBN) to yield a pair of free radicals R·, and the second the
addition of a monomer to the primary radical R· to yield the chain radical, which is called the
initiation. It was found that the rate-limiting step is the initiation step, that is, the rate constant
for initiator dissociation is much smaller than that for monomer addition.

Some of the monomers may also undergo other reactions such as combination with another
radical to form inactive molecules.

The efficiency of the radicals with which they initiate chains can be estimated by comparing
the number of initiators decomposed with the number of polymer chains formed, that is, only
a fraction f of the initiator concentration does initiate a polymerization process. Based on
observations, the rate of initiation is proportional to the concentration of initiators [I] and the
efficiency f:

Ri = d[M·] / dt = 2 f kd [I]

where kd is the rate constant (velocity coefficient) of initiation.

PROPAGATION

The growth of a polymer chain by successive addition of monomers during propagation can
be represented as follows:

RM1· + M → RM2·

RM2· + M → RM3·

And in general:

RMx· + M → RMx+1·

The general assumption is that the radical reactivity is independent of the chain length, this
means, that all the propagation steps have the same rate constant kp1 = kp2 = ... = kp. Thus,
the rate of polymerization equals the consumption of monomers in the propagation step.
Since both a monomer and the growing polymer chain are involved in the reaction, the
reaction rate is proportional to both concentrations.

Rp = -d[M] / dt = kp [M] [M*]

where kp is the reaction constant or velocity coefficient of the process and [M*] = ∑RMx,
which is the sum of the concentration of all chain radicals.
TERMINATION

The propagation step would theoretically continue until all monomers are consumed.
However, pairs of radicals also have a tendency to react with each other and thus annihilate
their activities. The termination can occur via combination or disproportionation. In the case
of combination or coupling, two growing polymer chains react with each other forming a
single nonreactive polymer chain:

Mx· + My· → Mx+y

And in the case of disproportionation, a hydrogen atom is transferred from one radical to the
other resulting in two polymers, one with a saturated end and the other with an unsaturated
end and each with an initiator fragment.

Mx· + My· → Mx + My

Usually, there is no need to distinguish between these two different types of termination
reactions, that is, both reactions can be combined to one rate expression:

Rt = -d[M·] / dt = 2 kt [M·]2

Where the factor two occurs as a result of the disappearance of two radicals at each incidence
of termination reaction.

QUES 2)
SOL.2
Polymerization reactions such as that shown for e-aminocaproic acid (A-B monomer) or
adipic acid (A-A monomer) with hexamethylenediamine (B-B monomer) can be written in
the general forms, as follows:

where N0 is the number of monomer molecules at the beginning of the reaction. At any given
stage of the reaction, if N or 2N functional groups, respectively, have remained unreacted,
then there will be N or 2N molecules in the mixture, regardless of size. The total number of
functional groups of either type A or B that have reacted is therefore No — N. The extent of a
reaction at a given stage of the polymerization is defined by P, which is the ratio of the
number of reacted molecules to the initial number of molecules.

P = (Nq — N)/N0
N = N0(l - P)
The degree of polymerization, DP is the original number of molecules divided by the
remaining number of molecules and approaches a number equal to the original number of
molecules as N approaches one.

Thus, the degree of polymerization can be expressed by

Consider a reaction that can be pushed to 90% completion. The number of times an organic
chemist realizes this yield in the laboratory is not very often. Yet polymer chemists must
obtain yields much better than this to produce high molecular weight step-growth polymers.

A decamer is not a high enough molecular weight material to have useful mechanical
properties. At DP = 50 many polymers begin to exhibit sufficient mechanical strength to be
useful materials. To realize this DP a 98% yield reaction is necessary!

What is the effect on DP of the presence of an impurity in the monomer or a stoichiometric

imbalance? For the polymerization of the A-B monomer, if there is a monofunctional
impurity, A, present, and N0 is the number of molecules of AB while iVi is the number of
molecules of A, then

With 2% of the impurity A, and a 98% conversion,

In this case, with the same conversion (98%) an impurity (2%) cuts the molecular weight in
half. A stoichiometric imbalance has the same effect on the molecular weight as does an
impurity. For the polymerization of an A-A monomer with a B-B monomer, if the mole ratio
of the two, r, is not one, the expression

shows the effect of this imbalance on the molecular weight. For a 98% reaction conversion
again, and a 2% excess of B-B (r = 0.98), DP = 33.

QUES 3)
SOL 3.
a)
CHAIN TRANSFER
Chain transfer is a termination reaction by which the free-radical site of a growing polymer
chain is transferred to another molecule:

Rr· + S → Pr + S·

The newly formed solvent or monomer radicals may then reinitiate chain growth by
resumption or propagation reactions:
 S· + M → R1·
R1· + M → R2 etc.

The amount of chain transfer to monomers is usually low because this reaction requires
breaking strong carbon-hydrogen bonds. However, there are some exception. For example,
vinyl chloride has a rather large chain transfer constant when compared to most other vinyl
monomers. The same is true for chlorinated solvents like chloroform and ethylene dichloride.
In many cases, the transfer of the radical takes place through the removal of an atom (H, Cl,
Br etc.). The reactivity depends on the bond strength between the labile atom that is
abstracted and the rest of the molecule. In general, the reactivity of a chain transfer increases
with increasing substitution at the α-carbon. For example, for vinyl monomers such as styrene
or methyl methacrylate the chain transfer increases in the order

Benzene < Toluene < Ethyl benzene < Isopropyl benzene

Common chain transfer agents are halogen compounds, like chloroform and carbon
tetrachloride, certain aromatic hydrocarbons, and thiols (mercaptans). These compounds are
often called modifiers or regulators. Very strong chain transfer agents like pentaphenyl
ethane, carbon tetrabromide, and certain mercaptanes, even when added in small amounts,
will have a strong effect on the final molecular weight, that is, with increasing amount of
regulator, the degree of polymerization sharply decreases.

Chain transfer can also occur within a poymer (intermolecular chain transfer), for example
from the terminal group to a location on the polymer backbone by hydrogen abstraction. This
reaction is known as backbiting. The result is branching of the backbone. In the case of
polyethylene (see figure below), this reaction leads to short branches of about four to five
repeat units.
Chain transfer not only depends on the type of transfer agent but also on the temperature and
polymer type. An increase in temperature almost always increases the amount of chain
transfer, thus lowers the molecular weight2, whereas the viscosity (i.e. polymer concentration,
degree of polymerization) and polymerization rate2 have no or only little effect on the rate of
chain transfer.

b)
Molecular weights

Molecular weights of PMMA samples with different chain transfer agents were measured by
Ostwald viscometer in chloroform at 30 C. The Mw of PMMA samples were calculated by following
formula.

where h is viscosity of solution of PMMA sample in chloroform and Mw is molecular weight of

PMMA sample.

Effect of chain transfer agent on molecular weight

Commercially available PMMA which is used for fabricating optical fiber is around 100,000e150,000
g/mol. Therefore, Mw of bulk polymer samples should be in this range and concentration of CTA
should be low as far as possible for avoiding impurities. CTAs which arrange polymer chains during
polymerization control the Mw. There is a relative inversely between concentration of chain transfer
agent and Mw of polymer.

Due to different reactivity of varied CTAs, it is caused to have different Mw of polymer samples
which were produced with same concentration of CTA.

According to molecular weight results, optimum CTA is n-BMC to produce polymer which is in
desired Mw range with lower concentration of CTA. It can be considered that optical loss due to
compounds besides PMMA in polymer structure was minimized. PMDS is also suitable CTA in this
range. In Fig. 2(a), minimum Mw of polymer sample which was produce with IPA was reached to
above of commercial PMMA and concentration of CTA was not increased due to avoid from optical
loss. In comparison of purified and non-purified PMDS, , it can be seen clearly that purified PMDS
has better slope than non-purified PMDS. Impurities could cause inhomogeneous polymerization.
Homogeneous polymerization is highly important to have proper polymer for optical fibre
technology.

Molecular weights of polymer sample with different concentration of CTAs (a: IPA, b: n-BMC, c:
Purified PMDS and d: non-purified PMDS)
c)

The degree of polymerization, or DP, is the number of monomeric units in

a macromolecule or polymer or oligomer molecule.
For a homopolymer, there is only one type of monomeric unit and the number-average degree
of polymerization is given by , where Mn is the number-average molecular weight and M0 is
the molecular weight of the monomer unit. For most industrial purposes, degrees of
polymerization in the thousands or tens of thousands are desired. This number does not
reflect the variation in molecule size of the polymer that typically occurs, it only represents
the mean number of monomeric units.
Some authors, however, define DP as the number of repeat units, where for copolymers the
repeat unit may not be identical to the monomeric unit. For example, in nylon-6,6, the repeat
unit contains the two monomeric units —NH(CH2)6NH— and —OC(CH2)4CO—, so that a
chain of 1000 monomeric units corresponds to 500 repeat units. The degree of polymerization
or chain length is then 1000 by the first (IUPAC) definition, but 500 by the second.

Correlation with temperature

Relationship between degree of polymerization and melting temperature for polyethylene.

Data from Flory and Vrij (1963).
Polymers with identical composition but different molecular weights may exhibit different
physical properties. In general, increasing degree of polymerization correlates with higher
melting temperature and higher mechanical strength.