04/09/2014

Lec-05
Stereo Isomerism

In a syndiotactic configuration, the R

groups alternate sides of the chain while
for random positioning, the term atactic
configuration is used.
Syndiotactic configuration

Atactic configuration

2. Stereo Isomerism

Another example of isotatctic polymers is polypropylene chains where all

methyl CH3 substituent are on the same side as shown in Figure.
But due to steric repulsion between adjacent methyl groups, the chain would
fold into a new orientation, in which some of the methyl groups take the
upper and lower side of the backbone carbon chain, which is syndiotactic.

04/09/2014

2. Stereo Isomerism

If the random arrangement results, it will be called atactic.

Another example is PVDF with -phase and -phase which are

stereoisomers.
Syndiotactic

Isotactic

3. Structural Isomerism

Or geometric isomerism, occurs where mer units have double bond between
carbon atoms. For example consider the isoprene repeat structure

In which the CH3 group and the H atom are positioned on the same side of
the double bond. This is termed a cis-structure, and the resulting polymer,
cis-polyisoprene, which is natural rubber.
In trans-structure, the CH3 and H reside on opposite

sides of the double bond. Trans-polyisoprene (gutta percha)

properties are different from natural rubber.

04/09/2014

Thermoplastic Polymers
The thermoplastics softens and can be made to flow when it is heated. This
allows them to be fabricated into the required component and become solid
when cooled to RT.

Thermoplastics consists of linear polymers which can not cross-link (although

may be branched) to form a rigid network. The bonding between chains is due
to the weak van der Waals forces.
Thermoplastics may be repeatedly heated and cooled, hence recyclable but
may degrade with repeated cycling unless stabilised.

Examples: Nylon(polyamide), polystyrene, polyethylene, polycarbonate, PMMA

(Perspex), PVC and PET

Thermosetting Polymers
Thermosets readily cross-link/network during curing by heat/pressure or by
a catalyst/curing agent/hardener. Bonding is covalent which restricts the
movements of chains past each other under stress or temperature resulting in
increase in the glass transition temperature Tg to above room temperature.

Due to the cross-linking, thermosets can not be re-shaped/resoftened by

reheating, rather they degrade on reheating. Thermosets are also found brittle
at room temperature. Ccomparably, thermosets are more resistant to chemical
attacks.

Examples of thermosetting polymers are Bakelite, Epoxies, Polyester,

synthetic Rubber, Polyimide etc.

Polyethylene and poly(vinyl chloride) wire coverings and pipe can be

converted to thermoset structures by cross-linking their molecules
photochemically (by high-energy radiation) or by decomposition of peroxides.
The main advantage of this cross-linking is enhanced dimensional stability
under load and elevated temperatures.

04/09/2014

Which polymers are these?

PE
Rubber
PMMA

Bakelite
PVC

PET

PS

Molecular Weight of Polymers

During polymerisation, not all polymer chains will grow to the same length.
This results in a distribution of chain lengths or MWs. Therefore the
molecular weight of polymers is expressed as average. There are two ways
to express it.
Number Average Molecular Weight

Is obtained by dividing the chains into series of size ranges and then
determining the number fraction of chains within each size range. It is
expressed as M n given by;
M n xi M i

Where Mi is the mean molecular weight of size range i, and xi is the fraction of
the total number of chains within the corresponding size range.

04/09/2014

Molecular Weight of Polymers

Weight Average Molecular Weight M w
Is based on the weight fraction of the molecules within various size ranges.

M w wi M i

Where wi denotes the weight fraction of the molecules within the same size
range.
Degree of Polymerization (DP)
Is the average number of repeat units in the polymer chain. DP is related to
the number-average molecular weight M n
by the equation

DP

Mn
m

Where m is the molecular weight of the repeat unit or mer.

Polydispersity of the polymer
Mw
PD
Tells us how broad the molecular size distribution is
Mn

Molecular Weight of Polymers

What we need to do is to make a list of Mi and xi to calculate the number

average MW as follows.

04/09/2014

Molecular Weight of Polymers

Mi (kg/mol)

xi

xiMi

Wi=xiMi/xiMi

7.5

0.05

0.37

0.37/21.14=0.02

12.5

0.16

2.0

2.0/21.14=0.09

17.5

0.22

3.85

3.85/21.14=0.18

22.5

0.27

6.07

6.07/21.14=0.29

27.5

0.2

5.50

5.5/21.14=0.26

32.5

0.08

2.60

2.6/21.14=0.12

37.5

0.02

0.75

0.75/21.14=0.03

No. average

xiMi=21.14
kg/mol
Weight avg.

Calculate wiMi , Mw , nn and nw?