Lecture Plan: Teacher-2

Lecture Topics
L1 General introduction
L2 Polymer: Classification and polymerizations
L3 Polymer: Mechanism of polymerization
L4 Polymer: Processing of polymer.
L5 Plastics: Fundamental characteristics, classifications
L6 Plastics: Raw materials and manufacture of plastics
L7 Plastics: Some typical examples of plastics and uses.
L8 Class Test-1
L9 Fibers: Types of fibers, raw materials, applications
L10 Fibers: manufacturing processes of synthetic fibres.
L11 Rubber: Sources of natural rubber
L12 Rubber: chemical treatment of latex
Rubber: synthetic reactions and properties of synthetic
L13
rubber.
L14 Class Test- 2
 Molecular Weight of Polymer

• Molecular weight, M: Mass of a mole of chains.

Low Mol. Wt.

high Mol. Wt.

• Polymers can have various lengths depending on the number of repeat
units.

• During the polymerization process not all chains in a polymer grow to

the same length, so there is a distribution of chain lengths i.e.
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. 61
 MOLECULAR WEIGHT DISTRIBUTION
 Mol. wt. distribution affects the properties of polymer. Low mol. wt.
polystyrene behaves differently from high mol. wt. polystyrene.

 A sample of polystyrene having narrow mol. wt. range (50,000-60,000)

exhibit different properties from one that have wide range (50-1,00,000);
though the average molecular weight is same.

Number average molecular weight

 The number average molecular weight is the total weight/mass
of the polymer sample divided by the number of molecules in
the sample.
Total mass of polymer NiMi
Number average mol. wt. Mn = =
Total number of polymer Ni

Ni = Number of molecules
Mi = Weight of each molecule = XiMi
NiMi = Total mass of polymer sample Number fraction = Xi
Mn =  (number fraction of each polymer x total mass of each polymer)
 Number average molecular weight
Ni Xi Xi  Mi
10
32
44
54
40
16
4

Xi = Number fraction of each type molecule

63
 Weight average molecular weight
Wt. ave. mol. wt. =  (weight fraction of each type polymer x mass of each type polymer)

Mw = wiMi

wi = Weight fraction of each type polymer molecule

Weight of each type polymer NiMi
= =
Total mass of polymer sample NiMi

 NiMi2
Weight average mol. wt. = wiMi =
NiMi

Ni = Number of molecules
Mi = Weight of each type of molecules
NiMi = Total mass of polymer sample
Weight average molecular weight
Ni
1
3
44
54
40
16
4

Wi = Weight fraction

65
Number-average molecular weight (n)
Weight-average molecular weight (w)
Example - a polymer sample consists of 9 molecules of
mw 30,000 and 5 molecules of mw 50,000

Consider the previous example - 9 moles of molecular

weight 30,000 and 5 moles of molecular weight 50,000

Consider the previous example - 9 g of molecular

weight 30,000 and 5 g of molecular weight 50,000
 MOLECULAR WEIGHT
5 polymer chains of equal length
each chain contains 40 repeating unit
Mass of one repeating unit = 28 (-CH2 CH2-)

Total number of polymer = 5

Total Mass = 28 x 40 x 5 = 5600
Mol. wt. of one polymer = 28 x 40 = 1120

Total mass of polymer

Number average mol. wt. =
Total number of polymer

NiMi 5600
= = = 1120
Ni 5
 MOLECULAR WEIGHT

Total number of polymer molecule = 5

Mol. wt. of each polymer molecule = 28 x 40 = 1120
Total Mass = 28 x 40 x 5 = 5600

Weight fraction of 1st polymer, X1 = 1x1120/5600 = 0.2

Weight fraction of 2nd polymer, X2 = 1x1120/5600= 0.2
So on…………. 3rd X3 = 1x1120/5600= 0.2
4th X4 = 1x1120/5600 = 0.2
5th X5 = 1x1120/5600 = 0.2

Weight average mol. wt. =  (weight fraction of each polymer x total mass of polymer)
= XiMi
= 0.2x1120 + 0.2x1120 + 0.2x1120 + 0.2x1120 + 0.2x1120
= 1120
 MOLECULAR WEIGHT
 5 polymer chains of different lengths
 Each chain contains different number of
repeating unit.
 Mass of one repeating unit = 25

Polymer no Mol. wt.

1 (violet) 50
2 (green) 450
3 (orange) 1000
4 (cyan) 1500
5 (blue) 3000
Total 6000

Total mass of polymer 6000

Number average mol. wt. = = = 1200
Total number of polymer 5
 Polymer no Mol. wt. wt fraction of each mol.
1 (violet) 50 1x50/6000 = 0.0088
2 (green) 450 1x450/6000 = 0.075
3 (orange) 1000 1x1000/6000 =0.16
4 (cyan) 1500 1x1500/6000 = 0.25
5 (blue) 3000 1x3000/6000 = 0.5
Total 6000

Weight average mol. wt. =  (weight fraction of each polymer x total mass of polymer)

= 0.0088x50 + 0.075x450 + 0.16x1000 + 0.25x1500 + 0.5x3000

=2065
 MOLECULAR WEIGHT
Polymer Number of polymer Mol. wt.
type mol.
(violet) 4 50
(green) 5 450
(orange) 3 1000
(cyan) 5 1500
(blue) 3 3000
 MOLECULAR WEIGHT DISTRIBUTION
total wt of polymer
Mn 
total no. of molecules

NiMi
Mn = Ni

 NiMi2
Mw = xiMi =
NiMi

Weight average mol. wt. =  (weight fraction x total mass of polymer)

72
Molecular weight distribution
Here are:
10 chains of 100 molecular weight
20 chains of 500 molecular weight
40 chains of 1000 molecular weight
5 chains of 10000 molecular weight

(10 100)  (20  500)  (40 1000)  (5 10000)

Mn   1347
10  20  40  5

(10 100 2 )  (20  500 2 )  (40 1000 2 )  (5 10000 2 )

Mw   5390
(10 100)  (20  500)  (40 1000)  (5 10000)

Mw
Polydisper sity  4
Mn
 Polydispersity Index (PDI)
 PDI is a measure of the distribution of molecular
mass in a given polymer sample.
 It indicates the distribution of individual molecular
masses in a batch of polymers.
 The PDI is calculated by dividing the weight average
mol. weight by the number average mol. weight .

PDI = Mw/Mn

The PDI has a value always greater than 1, but as the

polymer chains approach uniform chain length, the PDI
approaches to unity (1). For some natural polymers PDI
is almost taken as unity.
Molecular wt. distribution based on PDI

PDI is low (nearly 1) PDI is high (>> 1)

Calculation of PDI
Ni Xi Xi  Mi
10
32
44
54
40
16
4

Ni
10
32
44
54
40
16
4
Measurement of molecular weight of polymer

1) Functional-group (end-group) analysis

2) Membrane osmometry
3) Light scattering
4) Ultracentrifugation
5) Measurement of viscosity

Conditions to measure mol. weight

 Solubility of the polymer
 Involve extrapolation to infinite dilution
 Operation in a Theta solvent (ideal-solution behavior)
 Measurement of molecular weight of polymer

1) Functional-group (end-group) analysis

 Molecular-weight determination through group analysis requires
that the polymer contain a known number of determinable
groups per molecule.

 The long-chain nature of polymers limits such groups to end

groups. Thus the method is called end-group analysis.

 Since methods of end-group analysis count the number of

molecules in a given weight of sample, they yield the number-
average molecular weight for poly-disperse materials.

 The methods become insensitive at high molecular weight, as

the fraction of end groups becomes too small to be measured with
precision.

 Molecular weights above 25,000-50,000 is difficult to measure

due to lack of precision.
Polymerization

Book: Robert Ebewele, Chapter 2.

 Synthesis of polymer

Polymer molecules may be synthesized by four different methods:

(a) Addition polymerization (Chain reaction polymerization)

(b) Condensation polymerization (Step reaction polymerization)

(c) Ring opening polymerization

(d) Oxidative polymerization

(a) Addition polymerization
Addition polymerization may be defined as the process in
which monomer units are added together to form a polymer
molecule without losing any small molecules. For
example, conversion of ethylene to polyethylene.
n(CH2=CH2) → (--CH2-CH2--)n
Depending on the mechanism addition polymerization may be classified into
three classes. These are-

i. Free radical addition polymerization

ii. Cationic addition polymerization
iii. Anionic addition polymerization

Whatever may be the method, the addition polymerization consists of three steps:
i. Initiation
ii. Propagation and
iii. Termination
i) Free radical polymerization
 The polymerization reaction is initiated by the decomposition
of some organic and inorganic peroxides such benzoyl
peroxide, hydrogen peroxide, diazo compounds etc. The
decomposition is carried out by the application of heat or light.
Peroxides → Radical

 These radicals serve as the active centers and cause chain

propagation by combining with monomer.
Initiator activation

Initiation

Propagation
Propagation

Termination

Chain transfer