Chapter-4: Molecular Weight of Polymer

What is Molecular Weight of Polymer?

Molecular weight of polymer is defined as the sum of atomic
weight of each of the atoms in the molecules, which is present
in the polymer.

A polymer sample can therefore be thought of as a mixture of

molecules of the same chemical type but of different molecular
weights. in the situation the molecular weight of the polymer
sample can only be viewed statistically and expressed as some
average of the molecular weights contributed by the individual
molecules that make the sample.
 Different types of Molecular Weight
A polymer molecular weight can be expressed as following ways:
Number average molecular weight ( 𝐌 ഥ n): The number average molecular
weight is the total weight of the polymer molecules divided by the total number of
polymer molecules.
σ n iM i
ഥ
Mn = σ
ni
Weight average molecular weight (𝐌 ഥ w): The weight average molecular weight
is the ratio between the summation of the multiplication of molecular number and
square of molar weight divided by the total weight of the polymer.
2
n
ഥw = i iM
M σ n iM i

Viscosity average molecular weight (𝐌 ഥ v = σ viMi

ഥ v) : M
σ vi
3
σ n i Mi
Higher average molecular weight (𝐌 ഥ z):Mഥz =
σ n i Mi 2
 Importance of Polymer Molecular Weight

The influence of molecular weight on the bulk properties of polyolefin's, an

increase in the molecular weight leads to
Increase in:
1. Melt viscosity
2. Impact strength
Lowers in:
1. Hardness
2. Stiffness
3. Softening point
4. Brittle point

High molecular weight polymer does not crystallize so easily as lower

molecular weight material crystallizes due to chain entanglement and that
reflect in bulk properties of the high molecular weight polymer.
Degree of polymerization and its relation with M.W of Polymer?
Degree of polymerization is the ratio between the molecular weight of the polymer
and the molecular weight of the monomer.

M
DP =
m

Or, M = DP x m
Where DP is the degree of polymerization, M is the molecular weight of polymer, m is
the molecular weight of monomer.
Question-01: Find out the molecular weight of polypropylene(C3H6) with a DP of 3x104.
Solution:
So, Molecular weight of the monomer of polypropylene, m= 12x3+1x6 = 42 g/mole
∴ Molecular weight of polypropylene = DP x m = 3x104x42 = 1260000 g/mole.
Question-02: Calculate the molecular weight of polyisoprene (C5H8) if its DP is 5000.
[Do it yourself]
 Polydispersity

Most macromolecule materials where components have different

chain length thus different molecular weight is known as polydisperse
polymer. The characteristics of being polydisperse is called
polydispersity. It is a very important parameter which gives an idea
of lowest and highest molecular weight as well as the
distribution pattern of the intermediate molecular weight species.
 Monodispersity

Macromolecules where all components having same

chain length thus same molecular weight is known as
monodisperse polymer. The characteristics of being
monodisperse is called monodispersity.

Here, weight average molecular weight (Mw) is equal to

the number average molecular weight (Mn), hence
polydisperse index is 1. The polymer is perfectly
homogenous and uniform. All the molecules have same
size, shape and mass.
Example: Natural polymer are generally monodisperse.
 Index of Polydispersity
The ratio of weight average molecular weight to number average molecular
weight is called degree/index of polydispersity.
If, Mw = weight average molecular weight
Mn = number average molecular weight
Mw
Then, Polydispersity Index (PDI) = Mn
PDI=1 indicates Mw=Mn, [Ex: Monodisperse(all monomers have equal length]
PDI=1 is possible for only natural polymer.
1.5<PDI<5 is for synthetic polymers[Ex: Polydisperse].
 Index of Polydispersity
1
ഥn=
We have, Number average DP, X
(1−P)
1
∴ Number average molecular weight, Mn = M0Xഥn = ( 1−P
)M0 ………………….Eqn. 1
ഥw= 1+P
Again, Weight average DP, X
1−P
1+P
∴ Weight average molecular weight, Mw = M0Xw = ( )M0 ……………Eqn. 2
ഥ
1−P

From Eqn. 1 and Eqn. 2 we get,

Mw (1+P )M0 ( 1+P
) ഥ
X
Polydispersity Index (PDI) = = 11−P
= 1 = ഥw = (1 + P)
1−P
Mn ( )M0 ( ) Xn
1−P 1−P
 Index of Polydispersity
Example 2 : If M0 = C6H11NO = 113 and P= 0.995, PDI=?
H H
H2N-(-C-)5-COOH [---HN-(-C-)5-CO ---]n
H H

1 1
∴ Number average molecular weight, Mn = ( )M0
1−P
=
1−0.995
113 = 22,600

∴ Weight average molecular weight, Mw = (1+P

1−P
1+P
)M0 = ( )M0 = (
1−P
1+0.995
1−0.995
) 113 = 45,087

Mw 45,087
So, Polydispersity Index (PDI) = = = 1.995
Mn 22,600
 Index of Polydispersity
Example 1: Polymers containing the same amount (weight) of polymers A and B what is
the PDI?
Polymer A DP = 1000 Nx =10 Wx= Nx x Mx = 10x1000=10000 ഥ x =10/11
N ഥ x = 10000/20000
W
Polymer B DP = 10000 Nx =1 Wx= Nx x Mx = 1x10000=10000 ഥ x =1/11
N ഥ x = 10000/20000
W

∴ Number average DP, Xഥn = σ Nഥ x . DP =( 10

11
1
x1000 + x10000) = 1818
11
ഥ x . DP = ( 1 x1000 + 1 x10000) = 5500
ഥw = σ W
∴ Weight average DP, X
2 2
Xw 5500
So, Polydispersity Index (PDI) = = = 3.02
Xn 1818
 Mathematical Expression for Mn and Mw
In computing the molecular weight of a polymer we can use either the number
fraction or weight fraction of the molecules present in the polymer to get either the
number average molecular weight (expressed as M ഥ n) or the weight average
molecular weight (expressed as M ഥ w).
Let us consider a polymer sample having n molecules:

Fig: A polymer sample containing n number of molecules of different molecular

weights of which n1 have a molecular weight M1, n2 have M2 and so on.
 Mathematical Expression for Mn and Mw
1. Expression for 𝐌ഥn :
Total number of polymer molecules, n = n1 + n2 + n3 … … … … … ni = σ ni

Say, Number of molecules in polymer 1 = n1

∴ Number fraction of polymer 1 = σnn1
i
n1 n1M1
Now, Molecular weight contribution by polymer 1 = σ x M1 = σ
ni ni
Similarly, molecular weight contribution by other polymer will be as follows:
n2M2 n3M3 niMi
σ ni
, σ ni
, … … … … … … … σ ni

∴ Number average molecular weight (M ഥ n)= n1M1 + n2M2 + n3M3 … … … … niMi

σ ni σ ni σ ni σ ni
σ niMi
ഥ
or, Mn = σ
ni
 Mathematical Expression for Mn and Mw
ഥw :
1. Expression for 𝐌
Total weight of polymer molecules, w = w1 + w2 + w3 … … … … … wi = σ wi
= n1M1 + n2M2 + n3M3 … … … … … + niMi = σ wi
= σ niMi = σ wi
Say, Weight of polymer 1 = w1 = n1M1
w nM
∴ Weight fraction of polymer 1 = σ 1 = σ 1 1
wi niMi
2
nM nM
Now, Molecular weight contribution by polymer 1 = σ 1 1 x M1 = σ1 1
niMi niMi
Similarly, molecular weight contribution by other polymer will be as follows:
2 2 2
n2M2 n3M3 niMi
,
σ niMi σ niMi
, ……… ……… …σ
niMi
2 2 2 2
n M n M n M
ഥ w)= 1 1 + 2 2 + 3 3 … … … … … i i n M
∴ Weight average molecular weight (M σ niMi σ niMi σ niMi σ niMi
2
σ niMi
or, Mഥw =
σ niMi
 Mathematical Example for Mn and Mw
Example 1: Lets we had the following polymer sample [1 Dalton= 1 g/mole]. Calculate the number
average molecular weight and weight average molecular weight.
Polymer Chain Molecular Weight of Each Chain No. of Chain
1. 1,000,000 Dalton 2
2. 700,000 Dalton 5
3. 400,000 Dalton 10
4. 100,000 Dalton 4
5. 50,000 Dalton 2

Solution: Number average molecular weight (Mn):

Polymer M.W. of Each No. of Chain n ni
Number Fraction(σ ni ) σ ni
xMi
Chain Chain (Mi) (ni) i

1. 1,000,000 2 2/23 86956.52

2. 700,000 5 5/23 152173.9
3. 400,000 10 10/23 173913.04
4. 100,000 4 4/23 17391.30
5. 50,000 2 2/23 4347.82
Total = 23 σ niMi
σ ni
= 434,082
 Mathematical Example for Mn and Mw
σ niMi
ഥn =
∴M = 434,082
σ ni

Weight average molecular weight (Mw):

Polymer M.W. of Each No. of nixMi= Wi Weight fraction, nixMi
σ nixMi
x Mi
Chain Chain (Mi) Chain (ni) n xM
wi = σ i i
nixMi
1. 1,000,000 2 2,000,000 0.20 200,000
2. 700,000 5 3,500,000 0.35 245,000
3. 400,000 10 4,000,000 0.40 160,000
4. 100,000 4 400,000 0.04 4,000
5. 50,000 2 100,000 0.01 500
2
σ ni= 23 σ niMi= σ Wi = =1 σ niMi
σ niMi
= 609,500
10,000,000
2
σ niMi
∴ ഥ
Mw = σ = 609,500
niMi
 Mathematical Example for Mn and Mw
Example 2 : There are different types of vegetable in a box. Find out the number average molecular weight,
weight average molecular weight and index of polydispersity by following the data in the table.
Items Number of item Weight of each item
Onions 2 10
Brinjals 4 20
Cabbages 3 100
Cauliflower 3 250
Solution:
Items Number of Weight of each Number ni
σ ni
xMi
item (ni) item (Mi) n
Fraction(σ i )
ni
Onions 2 10 2/12 1.66
Brinjals 4 20 4/12 6.66
Cabbages 3 100 3/12 25
Cauliflower 3 250 3/12 62.5
Total= 12 σ niMi
σ ni
= 95.82
 Mathematical Example for Mn and Mw
Items Number of Weight of each nixMi= Wi Weight fraction, nixMi
σ nixMi
x Mi
item (ni) item (Mi) n xM
wi = σ i i
nixMi
Onions 2 10 20 0.017 0.17
Brinjals 4 20 80 0.070 1.4
Cabbages 3 100 300 0.261 26.1
Cauliflower 3 250 750 0.652 163
2
Total= 12 σ Wi = 1150 σ niMi
σ niMi
= 190.67

σ n i Mi 1150
i. ഥn =
M = = 95.82 ≡96
σ ni 12

2
ii. ഥ w =σ niMi = 190.67 ≡191
M σ n i Mi

ഥ
M 191
iii. Index of polydispersity = ഥw = = 1.98
M 96
 Mathematical Example for Mn and Mw
Example-03: What would be the average molecular weight of 1 elephant (10,000 lb) and
4 mosquitos (1 lb each)?
Solution:
σ niMi 1 4
ഥn =
i. M = ( 5 x10,000 + 5 x1)= 2000.8 ≡ 2,001
σ ni
2
σ niMi 1x10,000𝑥10000 4x1x1
ഥw =
ii. M =( + ) = 9996+0.0004 = 9996.0004 ≡ 9996
σ niMi 10,004 10,004
 Mathematical Example for Mn and Mw
Example- 04: What would be the number average of molecular weight and
weight average molecular weight of the polymer where 5 chains (10,000 lb each), 5
chains (15,000 lb each) and 5 chains (20,000 lb each)?
Example- 05: What would be the molecular weight of the polymer if 9 moles,
molecular weight is 30,000 lb each and 5 moles, molecular weight is 50,000 lb
each?
Example- 06: There are different types of vegetable in a box. Find out the
number average molecular weight, weight average molecular weight and index of
polydispersity by following the data in the table.
Items Number of item Weight of each item
Onions 4 20
Brinjals 6 100
Cabbages 3 250

[Do it yourself]
Instruments For Determining The Molecular Weight of Polymer
a) Absolute method:
i. End group analysis
ii. Colligative properties
❖ Membrane Osmometry
❖ Ebulliometry (boiling point elevation)
❖ Cryscopy (freezing point depression)
❖ VPO (vapor pressure osmometry)
iii. Ultra- centrifugation
iv. Light scattering
b) Relative method:
❖ Viscometry
c) Fractional method:
❖ Gel permeation chromatography (GPC)
❖ Mass spectrometry
 End group analysis
• End group analysis is a chemical method used for calculating the number average
molecular weight of the polymer whose molecule has a reactive functional group at
one end or both ends of the molecule.
• For example, we know the structure of carboxy-terminated polybutadiene (CTPB)
and hydroxy terminated polybutadiene (HTPB). These molecules have carboxyl
and hydroxyl groups at their respective ends. Each molecule possesses two
functional group. Thus functionality of CTPB and HTPB is two. Except this other
functional group may be aldehyde, ester, amino, methyl group etc.

HTPB
 End group analysis system
• Usual chemical method are employed to find out the total number of functional
groups presents in a given weight of the sample and this is expressed as a
functional group equivalent/100g.
• From a knowledge of the functional group equivalent and the functionality, the
molecular weight can be calculated using the equation:
Functionality
ഥn =
M
Functional group equivalent
• For instance, CTPB molecular weight can be determined as follows:
a. Commercial grade ethanol is distilled and neutralized with a dilute solution of alcoholic
KOH.
b. Then 1:3 mixture of ethanol and toluene is made.
c. A precisely weighted quantity less than 1 gm of CTPB sample is dissolved in the mixture.
This is titrated against a .01 N KOH solution. The end point slightly pink color.
Let us volume of KOH = V ml.
Normality of KOH =N
Weight of sample = W gm
 End group analysis system
VN x 56.1
Carboxyl value = mg of KOH/gm
W
VN x 56.1 100 VN
Carboxyl equivalent = x =
W x 1000 56.1 10W
• In a particular measurement if 0.8734g CTPB of the sample has consumed 5.1 ml of
0.1242 N KOH solution, then,
VN 5.1x0.1242
Carboxyl equivalent = = = 0.0725
10W 10x0.8734
Assuming a functionality 2, we get
Functionality 2x100
ഥn =
∴M = = 2760
Functional group equivalent 0.0725
 Considering point in End group analysis
• End group are commonly used and can be analyzed by nuclear magnetic
resonance (NMR) spectroscopy to determine the average length of polymer.
• In this method the polymer weight limited up to 50,000.
• Thus, this method is not suitable for high molecular weight because the fraction of
end groups becomes too small to measured with precision.
• The method cannot be applied to branched polymers.
• In a linear polymer there are twice as many end of the chain and groups as polymer
molecules.
• End group analysis could be applied for polymerization mechanism identified
 Gel Permeation Chromatography (GPC)
• It was first developed in 1955 by Lathe and Ruthven.

• GPC is an analytical technique that separates molecules in polymer by size.

• It provides the molecular weight distribution of a material.

• GPC is also sometimes known as size exclusion chromatography (SEC)

 Principle of Gel permeation chromatography (GPC)
• GPC operates on the principle that polymer molecules in solution separate according to their
size and not chemical interaction.
• When a dilute solution of the polymer sample in a solvent starts streaming down the column,
the mobile phase around the gel beads contains the polymer molecules, whereas the
stationary phase within the gel beads does not contain any.
• Due to this difference in polymer concentration between the mobile phase and stationary
phase polymer molecule start diffusing into the stationary phase(pore volume). Although all
polymer molecule try to enter but pore size restricts the entry and allows lowest molecular
weight polymer to enter only. Molecules of big size and large molecular weight are thus
washed down and eluted the column by the solvent. Intermediate size polymer diffuse slowly
and occupy only limited pore area.
 Principle of Gel permeation chromatography (GPC)
• As the column is eluted further with a pure solvent, the mobile phase becomes devoid of
polymer molecules, whereas the stationary phase contains a large quantity.
• This difference in concentration now reverse diffusion start from stationary phase to mobile
phase. In this process smallest molecular weight polymer are retained in the column
maximum time and eluted last.
• If we denote the pore volume by Vp and the void volume by Vv, then the largest molecules,
which are totally excluded from the pore area elute out of the column when a solvent volume
equal to Vv. The smallest molecules which permeate the maximum volume of pore elute out
at a volume of (Vv+Vp). The intermediate size molecules elute between Vv and (Vv+Vp).
• Hence the elution volume directly gives an estimates of the molecular size.
 How Gel permeation chromatography (GPC) works?
➢ Inject the sample into continuously flowing mobile phase of the same solvent.
➢ Your dissolved sample and mobile phase is then pumped through a column.
➢ From elution volume between polymer solution and pure solvent we measure the refractive
index value. This refractive index difference directly gives the concentration of the polymer
eluted.
➢ With the known elution volume and refractive index and by comparison with calibration curve,
we can directly get the molecular weight of polymer.
➢ Data are processed and recorded in the form of a plot of elution volume vs recorder output of
differential refractometer. The plot directly gives the molecular weight distribution.
 Components of Gel permeation chromatography (GPC)
1. GEL: Used as stationary phase and no ionizing group present in its and having low
affinity for the substance to be separated. They are packed into column.
2. SOLVENT: Choosing an appropriate solvent for your sample is very important. It may be
non-polar to aqueous in nature.
3. INJECTOR: Most GPCs have an auto sampler with an injector. Using an auto sampler,
you can set up a very large run and let it run overnight.
4. COLUMN: A GPC column is made up of the mobile phase and stationary phase of porous
particles all packed together into a column. GPC column separate material by size, higher
molecular weight material passes through the column first, while lower molecular weight
material enter the pores and takes longer to elute out of the column.
5. PUMP: The pump pushes the mobile phase and your samples through the column. Pump
pressure and flow rate are two very important variables in GPC. A flow rate that is too
slow makes the test unnecessarily slow, while a flow rate that too fast can provide
inaccurate measurements.
6. DETECTOR: Numerous types of detector also exist for GPC, including ultraviolet,
refractive index, infrared etc. normally two detector ae used in conjunction with each
other, so that molecular weight can be directly calculated.