An Introduction to Polymer Chemistry

GENERAL PHYSICAL AND CHEMICAL PROPERTIES, KINETICS AND MECHANISMS OF

POLYMERIZATION AND UNIT

DEPARTEMENT OF CHEMISTRTY
FACULTY OF MATHEMATICS AND NATURAL SCIENCES
HASANUDDIN UNIVERSITY
MAKASSAR
2017
1. GENERAL PHYSICAL PROPERTIES

If both systems are mixed ie G1 and G2 at constant temperature and

pressure, there will be physical or chemical changes, which will result in a
mixed G value less than G1 + G2. This can be written in the equation:

ΔG = Gfinal – Ginitial

always negative for spontaneous changes.

ΔG which occurs in mixed polymers and solvents is defined as:

ΔGmix = ΔGsolution- (Gpolymer + Gsolvent)

 This value depends on 3 factors, ie heat released in mixed polymers and
solvents, temperatures, and parameters that measure the increase in
interference due to mixing of polymers and solvents. At constant temperature
and pressure, it can be shown

ΔGmix = -Qmix –TΔSmix

It can be said that the solubility process has a positive ΔSmix. Therefore, at a
certain temperature ΔGmix will be negative.
The conditions required for the solution actually occur if

a. Gmix is +, i.e heat is applied to the thermostat on the solvent of the polymer
in the solvent;

b. Qmix is 0; i.e heat is not obtained from dissolving the polymer in the solvent;

c. Gmix is -, i.e some heat is absorbed from the thermostat but not sufficient to
compensate for the TΔSmix product.

This equation is usually written ΔGmix = ΔΗmix - TΔSmix but ΔHmix is identical to -Qmix
at constant pressure.
2. GENERAL CHEMICAL PROPERTIES

The chemical properties of a polymer depend, of course, on its structure; as

a general rule, a polymer shows the same reactivity towards a given reagent
as a low molecular weight compound with a similar structure to the
repeating unit of the chain. For example, the reaction of polystyrene

with bromine is similar to that of toluene

If the polymer is unsaturated, it can be hydrogenated or brominated under similar
conditions to those used for simple olefins, natural rubber and gutta percha, are
geometrical isomers; both give the same product on hydrogénation.
3. KINETICS AND MECHANISMS OF POLYMERIZATION

In the first reaction type, the monomers n molecules represented by M symbols

may or may not be identically converted into polymer molecules containing n
mers, Μ^, with the removal of simple molecules (n - 1) represented by the symbol
A. This reaction is called the condensation polymerization. One specific example
of a Reaction condensation polymerization would be sufficient at this stage.
The second reaction is called additional polymerization since the polymer is formed
by an monomer mol n n (which again may or may not be identical) join together in
this case, the number of atoms in the mers is equal to that of the monomer. Two
examples of the addition of polymerization reactions are given below:
In each example, the polymer chain has two ends of the group to satisfy the
valence requirements of the terminal mers. The first example illustrates perchloric
perchloric acid polymerization of styrene; Perchloric acid is added to the
polymerization styrene to continue at a limited level and at the end the reaction
can be recovered. The second example illustrates the polymerization of methyl
methacrylate initiated by benzoyl peroxide as the reaction progresses, this material
vanishes From the system, the fragment appears as the polymer end group.
Substances acting in this way are called initiators to distinguish them from
recoverable catalysts unchanged at the end of polymerization. This stoichiometric
equation, whether referring to the condensation or addition of polymerization,
does not tell anything about the mechanism of the reaction.
 In many polymer solvent systems, positive or zero Qmix of the entire
range of compositions and complete completeness is observed. However,
in many other cases, Qmix is always negative under certain temperatures.
The greater the value -Qmix the higher the critical temperature value of the
solution. For example, high -Qmix values are usually observed with semi-
crystalline polymers because large amounts of heat are required to break
up the crystal regions.

Therefore, higher temperatures are required to produce high solubility in

semi-crystalline polymer solvent systems than on mixtures containing
amorphous polymers. Linear and branched polymers can usually be
obtained in solution if the solvent and temperature are correctly selected.
a study of polymerization of methyl methacrylate (M) initiator benzoyl peroxide
(RO) initiated in this way would yield two phrases:
Where k0 and k'0 are numeric constants. The differential form of the level
expression indicates that this equation refers to a certain moment when the
concentrations of both reactants are [ROOR] and [M], the negative signals
indicate that the two species have decreased concentration. We summarize
this phrase with the term order. The level of loss of initiator is first order with
respect to the initiator (aproportional to the concentration of the initiator) and
the zero order with respect to the monomer (regardless of monomer
concentration); also, monomer loss rate is half order with respect to the
proponent, and the first order with respect to monomers.
The most important ois the coception tht a complex reaction such as
polymerization is made uo of a series of elementary reactions in which only one,
two or three molecules take part. Example:
Then all theories of reaction rates suggest that:

In the case of polymerization, a note of caaution, however, must be

sounded, it does not follow that a particular reaction sequence is the
correct mechanism simly because its kinetic consequences match the
experimental observation the agreement simply means that the
mechanism is possibility.
4. UNIT

In general to avoid confusion, we have adopted the following

conventions in dealing with quantities possessing units:
1. no units are attached to symbols
2. all arithmetical quantities which possess units are written explicitly
with the units
3. units where they appear in an expression are treated exactly as
algebraical symbols.
Let us see how these rules work in an actual case. A convenient example is
Poiseuille's expression for the volume rate of flow of a liquid through a tube. This
equation is:
𝜋𝑃𝑟 4
𝑣=
8ɳ𝑙
−2
π x 104 x ሺ2 x 10 )4 dyne cm−2 cm4
𝑣=
8 x 6 x 10−3 x 12 poise cm

The units of the final answer result naturally from this derivation.
5,23 𝑥 10−5
= 𝑔 𝑐𝑚2 𝑠𝑒𝑐 −2
ɳ
Formulation to calculate volume rate of flow (𝑣) for a liquid of any viscosity under
the same pressure

π x 104 x ሺ2 x 10−2 )4 dyne cm−2 cm4

𝑣=
8 x ɳ x 12 cm

5,23 x 10−5
= g cm2 sec −2
ɳ

On substituting the numerical value of ɳ and its units into this equation, we obtain
𝑣 in the usual unit of cm3 sec-1
One final example will suffice; suppose we wish to calculate the weight of a molecule of a
particular substance given its molecular weight M and the Avogadro number N.

𝑀
𝑚=
𝑁°
Given that M = 100 g mole-1 , we write

100
𝑚= g mole−1
𝑁°

100 g mole−1
𝑚=
𝑁° mole−1
𝑚 = 1,66 𝑥 10−22 g