Industrial Polymer

CHAPTER 4

Thermodynamics and Kinetics of

polymerization and polymer
molecular weight

Demis Zelelew (PhD)

January, @2024
05/11/2024 Hossana; Ethiopia
Kinetics of polymerization and polymer molecular weight
Point for discussion
Step-wise polymerization:
o Is relatively a slow process. Why?
o Any two monomers present in the reaction mixture can link together at any
time.
o The growth of the polymer is not confined to chains that are already
formed.
Chain polymerization:
oAn activated monomer attacks another monomer, links to it, then that unit
attacks another monomer, and so on.
oIs relatively a faster process. Why?
Main points of the chapter
• Kinetic chain length and degree of polymerization
• Polymer molecular weight:
o Number Average Molecular Weight
o Weight Average Molecular Weight
 4.1. Kinetic of polymerization
🖝Points for discussion

o What do you understand by the concepts “Thermodynamics and Kinetics of

chemical reactions?
o Why we need to worry about reaction kinetics?
o Is there any correlation between reaction kinetics and MW of a polymer?
o Discuss the differences between step polymerization and chain growth
polymerization. Which one is faster? Why?
 Thermodynamics tells us where the system would like to go eventually whereas
Kinetics tells us how fast the system takes various reaction paths. ??????
 In this section the reaction kinetic expressions of the following polymerization
processes will be discussed briefly
i.Step-growth or condensation polymerization
ii.Chain growth polymerization (e.g., Free radical polymerization)
iii. Copolymerization
4.1.1. Step-wise polymerization (linear high molecular weight polymer)

In this type of polymerization, the molecular weight of the polymer chain builds
up slowly and there is only one reaction mechanism for the formation of polymer.
O The distinct initiation, propagation, and termination steps of chain-growth
polymerization are meaningless in step-growth polymerization.

A difunctional monomer or equal molar amounts of two different difunctional

monomers are necessary at least to form a linear high MW polymer with
elimination of by-product.
The polymerization reaction proceeds by individual reactions of the functional
groups on the monomers (This reaction takes long time to get high MW polymer
or completion of the reactants)
Example, The formation of nylon-66

H2N(CH2)6NH2 + HOOC(CH2)4COOH →H2N(CH2)6NHOC(CH2)4COOH

HO-M-COOH + HO-M-COOH → HO-M-COO-M-COOH + nH2O
There are three critical requirements for the step-growth
polymerization to yield a
high molecular weight linear polymer (e.g., from difunctional monomers).
i. a perfect stoichiometric balance of the two difunctional monomers
ii. high degree monomer purity is necessary (for instance, a monofunctional
impurity may act as cap to stop polymerization process. ???)
iii. the reaction responsible for the polymerization must be a very high yield
reaction with the absence of side reactions.
🖝 If the monomer functionality is greater than two, then these requirements do
not apply, and the resulting polymer is either highly branched or a cross-
linked, three-dimensional network. ??????
 Example on formulation of kinetics of polymerization

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 No is the number of monomer molecules at the beginning of the

reaction.
o 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.
O The total number of functional groups of either type A or B that have
reacted is, therefore, No - N.
o 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.
 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

For example, the DP of a polymerization reaction with 90% completion is

For a polymerization reaction DP = 50, the yield of the reaction is 98%

Example
 If the reaction of a diol with a diacid to form a polyester is considered,
with no acid catalyst added, the diacid acts as its own catalyst, and third
order kinetics are observed.

o Where [C02H] and [OH] are the concentrations of

the carboxylic acid and alcohol functions,
respectively.
o If good monomer balance is achieved, then [C02H]
= [OH].
o If these concentrations are expressed in terms of C, then -dC/At = kC3 and
integration gives 2kt = (1/C2) - const.
o To express C in terms of the extent of the reaction, P, C = Co(l - P) and 2kt =
1/[C0(1 - P)]2 - const., where Co is the initial concentration of carboxyl or
alcohol functions.
o Thus, 2Co2kt = 1/(1- P)2 - const., and a plot of 1/(1 - P)2 versus t yields a
o
If, however, a strong acid catalyst such as p-toluenesulfonic acid is added to
the above polymerization reaction, the rate equation is -dC/dt = kC2 and
integration gives 1/C = k't - const.
Using the relationship C = Co(l - P), 1/C0(1 - P) = kt - const., or C0k't = 1/(1-
P),
The second order reaction of a glycol with adipic acid at 109°C with 0.01
percent of p-toluenesulfonic acid (based on carboxyl functions) gives a
polymer of DP 48 (Mn
~ 13,500) after five hours (Fig. 1,B). ????????
4.1.2 Kinetics of chain polymerization
Occurs by addition of monomers to a growing polymer, often by a radical chain
process.
Rapid growth of an individual polymer chain for each activated monomer. ????
o Example:The addition polymerizations of ethene, methyl methacrylate, and
styrene.
The rate of polymerization is proportional to the square root of the initiator
concentration.

The three basic types of reaction step in a chain (free radical) polymerization
that should
be considered are
(a) Initiation: I → R. + R. vi = ki[I]
M + R. → .M1 (fast)
(b) Propagation: M + .M1→ .M2
M + .M2→ .M3
vp = kp[M][.M]
(c) Termination:
o mutual termination: Mn + .Mm→ Mn+m

o disproportionation: . Mn + .Mm→ Mn + Mm

o chain transfer: M + .Mn → Mn + .M

Influences of termination step on the polymerization or kinetics of termination

step
•Mutual termination: two growing radical chains combine. vt = kt ([.M])2
• Disproportionation: Such as the transfer of a hydrogen atom from one chain
to another, which corresponds to the oxidation of the donor and the reduction
of acceptor. vt= kt ([.M])2

Reading assignment
Discuss the kinetics of copolymerization process with suitable
 4.2. Polymer molecular weight (MW)

Points for discussion

1.What is molecular weight?
2.Why we need to determine molecular weight of polymers?
3.How does MW of a polymer affect its mechanical properties?
4.Do two polymers with the same MW have the same properties??
 Polymer MW is important because it determines many physica
properties such as molecular weight, physical states, elasticit and tensile
strength. So, the control of the molecular weight of polymer is essential for
the production of products with different end uses. ????
• For example

The melting temperature increases with increasing MW. ????

At rt, polymers with very short chains (roughly 100 g/mol) will exist as liquids.
•Those with weights of 1000 g/mol are typically waxy solids and soft
resins. ???
•Solid polymers range between 10,000 and several million g/mol. ?????
Increase in molecular weight also
Increases the viscosity of the material. i.e., The longer the chains, the
harder it is to get
them to flow
Increases the weather resistance of the material.
As the chains are longer, so they can withstand
more damage before the mechanical properties will
start to diminish
 Increases the impact resistance of the material
Increases ductility
Lower MW polymers are brittle and also
have low mechanical strength.
?????
o Example, a candle and Polyethylene (PE)
have basically the same molecular structure.
The chain length of the candle is just much
shorter than that of the PE. If you bend a bar
of PE in half, it will bend. But if you bend a
candle in half, it will fracture.
Discuss: thereshold molecular weight of a polymer.?????
All polymers are mixtures of individual polymer molecules of variable MWs
depending on the number of repeat units. ?????

As discussed above, the polymerization process is subject to variation so there is

no single chain length, there is actually a wide range of lengths, so when we
discuss MW, we actually/really mean the average molecular weight of the
material. i.e., not all chains in a polymer grow to the same length, so there is a
distribution of molecular weights. There are several ways of defining an
average molecular weight.

•The molecular weight distribution in a polymer describes the relationship

between the number of moles of each polymer species and the molar mass of
that species.
Two types of molar mass distributions or two ways to calculate
the average molecular weight

(i) Number average MW (Mn): measured to determine number of particles or

Count the number of chains of a particular MW (Ni moles), multiply each
number by the MW (Mi), sum these values, and divide by the total number of
polymer chains. Where, xi = number fraction of chains in weight range i.
Mi = the middle of the ith weight range

Number average MW (Mn) is determined using methods that

include osmometry, centrifugation and batch light scattering. ????????
(ii) Weight Average Molecular Weight (Mw)

Consider of polymer property which depends not just on the number of polymer
molecules but on the size or weight of each polymer molecule.
This can be determined by using Light Scattering Measurement(Tyndall effect). ??

Where, wi = weight fraction of chains in size range I in the ith

range Mi = the mean (middle) of the ith weight range
The Weight Average Molecular Weight (Mw) is almost always higher than the
Number Average Molecular Weight (Mn). Why? What does this indicate?
 Weight Average Molecular Weight
Mw: Since most of the polymer mass is in the heavier fractions, this gives
the average molecular weight of the most abundant polymer fraction by
mass.
Exercise 1. Based on the following data to calculate Number average
molecular weight. Show steps.
Exercise 2. Based on the following data to calculate Molecular- average
molecular weight. Show steps
Exercise 3.
Measurements on two monodisperse fractions of a linear polymer, A and B, yield
molecular weights of 100 000 and 400 000, respectively. Mixture 1 is prepared from
one part by weight of A and two parts by weight of B. Mixture 2 contains two parts
by weight of A and one of B. Determine the weight- and number-average molecular
weights of mixtures 1 and 2.

Solution.
For mixture 1
 Solution.

For mixture 2

Exercise 4. Two polydisperse samples are mixed in equal weights.

Sample A has M n = 100 000 and Mw = 200 000.

Sample B has Mn = 200 000 and Mw = 400 000. What
are Mn and Mw of the mixture ?
Solution. First, let’s derive general expressions for calculating the averages
of mixtures:

Where the subscript i refers to various polydisperse components of the

mixture.
Now, for a given component,
Where ( Wi / Wi) is the weight fraction of component i in the mixture. In this case,

Let WA =1 g and WB = 1 g. Then

Note that even though the polydispersity index of each component of the
mixture is 2.0, the PI of the mixture is greater, 2.25. (show the steps)
 Polydispersity index (PDI or )

Polymers consists of many molecules of varying sizes or molecular

weights.????
The dispersity index () of the mass distribution is given as Mw/Mn measures
the extent of different molecular weights or used as a measure of the broadness of
distribution of molecular weights of a polymer
If the molecules in the mixture have an inconsistent size, shape and mass
distribution,
the mixture is called polydisperse.
PDI is greater than or equal to 1.0 (Why?)
A monodisperse sample (a polymer of the same size) ideally has Mw=Mn.
PDI = 1. Why?
So,
Example 2.
If two polymers of molecular weights 10,000 and 100,000 are mixed together in
equal parts by weight, determine the number average and weight average
molecular weights
(ii) The above polymers are mixed so that equal number of molecules are added,
Determine Mn and Mw.
Solution
(i) If equal parts of the two polymers of molecular weight
M=100000 and M=10000 are mixed, by definition

Reading assignment
Mn is sensitive to molecules of lower molecular weight whereas Mw is sensitive
to molecules of higher molecular weight. What are the possible
reasons?
Degree of polymerization, DP

 The degree of polymerization, or DP, is usually defined as of monomeric

units in a macromolecule or polymer molecule.
where n  repeat unit molecular weight
Example 1.

Determine DPn for PVC with the observed MW of 21,150 g/mol.

Mass of monomer : Mo = 2(carbon) + 3(hydrogen) + 1(Clorine)

= 2(12.011) + 3(1.008) + 1(35.45)
= 62.496 g/mol
DP = 21,150 / 62.496 = 338.42
Example 2.
Determine DPn for Poly vinyl acetate polymer that was made of 2000 monomeric
units.

1.The closer Mn is to Mw, the narrower the molecular weight spread. What does
this indicates?
2.Step polymerization reactions typically yield values of Mw/Mn of around 2.0,
whereas chain reactions yield Mw/Mn values between 1.5 and 20. How do you
explain such differences in Mw/Mn?
3.Calculate the MW for a polymer sample comprising of 9 moles of polymer
molecules having molecular weight of 30.000 g/mol and 5 moles of polymer
molecules having molecular weight of 50.000 g/mol.
🖝Effect of Polydispersity on a Polymer
As the broadness of the distribution decreases the
strength and toughness of the polymer increases.
However as the broadness of the distribution
decreases the polymer becomes more difficult to
process.
05/11/2024