SRI GURU TEG BAHADUR

KHALSA COLLEGE

Name- Deeksha Thakur

Course- B.Sc (Hons) Chemistry
Roll Number- 2018CHM1022
Semester- VI
Subject- Polymer Chemistry
Assignment
Submitted To: Dr. Manpreet Kaur
Topic- End group analysis for
Determination of Molecular weight of
polymers
Molecular weight of polymers:
If we think about the molecular weight of any organic molecule, we can
calculate the same from their molecular formulae. But what's about the
molecular weight of a polymer? As we know that during the polymerization
process, the growth of the chain is random in nature and the product contains a
mixture of chain of different length. As in a polymer, there is a spread or
distribution of different polymer molecules of different chain length, hence the
molecular weight of the polymer is given as an average molecular weight.
Different methods of determination of molecular weight provide different
average molecular weight.

The methods of determining molecular weight of polymers are of two types:

1. Primary or absolute methods: This method is capable of determining the

molecular weight from the principles of colligative properties and light
scattering methods.

2. Secondary of relative methods: In this method, requires calibration with the

sample of known molar mass

Molecular weight of polymers:

Regarding the molecular weight of a polymer, we will discuss three types of
molecular weight-

Number average Molecular weight (Mn),

Weight average molecular weight (Mw) and

viscosity average molecular weight (Mv).

Number average molecular weight (Mn): A polymer solution of known

concentration is made by dissolving a weight of amount of polymer in its
solvent. The colligative properties of this solution are then determined which
counts the number of molecules in a given volume or mass. Each Molecule
makes an equal contribution to the colligative properties regardless of its weight
or mass. Hence this method depends on the number of the molecule present.
The molecular weight obtained by colligative property measurement is known
as number average molecular weight and denoted by Mn. Thus Mn is
determined by Osmometry (Osmotic pressure measurement), Ebullimetry
(elevation of boiling point measurement), Cryoscopy (Freezing point depression
measurement) and end group analysis.

If a sample contains Ni molecules of molecular weight Mi, the number average

molecular weight is given by

Mn bar = ΣNiMi / ΣNi

Weight average molecular weight of polymers:

The weight average molecular weight is given by

Mw bar = ΣWiMi / ΣWi = ΣNiMi 2 / Σ NiM

A Higher Order MW, called the Z average, is closely related to processing
characteristics ⇒ a = 2

Mz bar = ΣNiMi ^(2+1) / Σ NiMi^ 2 = ΣNiMi^ 3) / Σ NiMi ^2

Viscosity average molecular weight (Mv):

The viscosity average molecular weight is obtained form the measurement of

viscosity and is given by-

A viscosity based

MW, Mv bar, has 0 ≤ a ≤ 1 and closer to 1 (i.e., to Mw bar)

MV bar = ΣNiMi (1.x) / Σ NiMi 0.x

1. Where x is typically close to 1 and ∴ 1.x is typically close to 2
2. ∴ MV bar = ΣNiMi (1.9) / Σ NiMi 0.9 in a typical case
3. Mz bar ≥ Mw bar ≥ Mv bar ≥ Mn bar

Where Ni is the number of molecules of molecular weight Mi, α is the

exponent in the Mark-Howkin-Sakurada equation, [η] = KMα where η is the
intrinsic viscosity., When α = 1 then Mv= Mn; Generally the value of α is 0.5<
α< Mw The value of α varies with polymer, solvent and temperature systems.
End Group Analysis:
The end group analysis is a chemical method used to determine the number
average molecular weight of a polymer sample through the analysis of reactive
functional groups at one end or both end e.g. Carboxyl terminated
polybutadiene, hydroxyl terminated polybutadiene. Apart from hydroxyl and
carboxyl groups, other end groups ( aldehyde, amino, ester) can possibly be
present in various polymers. For detecting and analyzing quantitatively
functional end-groups of linear polymer (nylon), the amino end-groups of nylon
dissolved in m-cresol are readily determined by titration with a methanolic
perchloric acid solution. Other titratable end groups are the hydroxyl and
carboxyl groups in polyesters and the epoxy end groups in epoxy resins. The
sensitivity of this method decreases as the molecular weight increases. This
method is limited to the determination of polymers with a molecular weight of
less than about 20,000.

From the knowledge of functional group equivalent and functionality, the

molecular weight can be calculated using the following equation

Mn = 𝐹𝑢𝑛𝑐𝑡𝑖𝑜𝑛𝑎𝑙𝑖𝑡𝑦 /𝐹𝑢𝑛𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑔𝑟𝑜𝑢𝑝 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛t

Example: The carboxyl value of cabroxyl terminated polybutadiene
(CTPB) can be determined by dissolving a known amount of the polymer in
a mixture of toluene and ethanol (1:3) and titrating against alcoholic KOH
using phenolphthalein indicator.

Let, the volume of KOH consumed= V ml;

Normality of KOH= N; and

Weight of the sample taken= w g

Carboxyl value = 𝑉 𝑥 𝑁 𝑥 56.1/ 𝑤

Carboxyl equivalent/100g = 𝑉 𝑁 56.1 × 100 /(𝑤 (1000) × 56.1)

In a particular measurement, if 0.8734 g of the sample has consumed 5.1 ml 0f

0.1242 (N) alcoholic KOH solution then

Carboxyl equivalent/100g = 5.1 ×0.1242 /(10×0.8734) = 0.0725

Assuming functionality of 2,

Number average Molecular weight; Mn = 2 ×100 0.0725 = 2760

The chemical analysis method is limited to the insolubility of the polymer in

the solvent.
One of the challenges polymer scientists face is molecular weight
(average chain length) determination of their materials. While
membrane osmometry, gel permeation chromatography, viscosity
analysis and mass spectrometry are typically used for molecular
weight determination, the techniques can be time consuming,
inaccurate for the molecular weight ranges involved, or require
specialized instrumentation.
End-group analysis by NMR offers an easy alternative method using
an instrument commonly found in many analytical labs.
In addition, NMR analysis can also be used to accurately determine
monomer ratios for various copolymer.
Scientists at Sigma-Aldrich routinely determine number average
molecular weight (Mn) by 1H NMR end-group analysis for polymers
having Mn values under 3000.
Sensitivity of the instrument to detect end-group protons will
determine the upper limit that can be measured. In order to use this
method, the following criteria must be met:
• Identifiable end-group protons distinguishable from repeating
monomer-group protons by NMR
• Accurate integration of both end-group and monomer protons
• Knowledge of monomer formula weights
Once the ratio of protons on the end-groups to protons on the polymer
chain is determined, using the NMR, simple math can be applied to
generate the Mn value. This example illustrates this method:

1) Calculation, integral per proton: Locate the end-group proton signals (ca. 5.8,
6.2 & 6.4 ppm) integral per proton = sum of vinyl proton integrals # of protons
in the two vinyl end groups (10.00 + 9.66 + 10.17)/6 = 4.97 per proton
2) Calculation, number of repeating monomer units, n:
Locate the OCH2CH2 proton signals (ca. 3.6, 3.7 & 4.3 ppm)
n = ((sum of CH2 proton integrals)/# of CH2 protons)/{integral per proton
value}
((20.79 + 151.87)/4)/4.97= 8.69 repeating units, n;
3) Calculation, Mn:
Mn = (FW end groups) + (FW repeating unit)(n)
= (55.06 + 71.60) + (44.05)(8.69) =509;
Therefore, the Mn of this polymer is approx. 509
End-Group Analysis
i) Basic principles

A. The structures of the end groups must be different from that of the bulk
repeating units (e.g., CH3 vs. CH2 in an ideal polyethylene)

B. ∴ If you detect the concentration of the end group and know the total amount
of sample present you can calculate the average MW, Mn bar

1. need to have either a perfectly linear polymer (i.e., two end groups per chain)
or need to know information about the amount of branching

2. ∴ the Mn bar values that come out for “linear” polymers must typically be
considered an upper bound since there may be some branching

C. Detection of concentrations of end groups

1. Spectroscopy - IR, NMR, UV-Vis

2. Elemental Analysis

3. Radioactive or Isotopic labels

ii) Strengths

A. The requisite instruments are in any department

B. can be quite quick Sometimes this information comes out “free” during
polymer structural studies Weaknesses does not give MW distribution
information need to know information about the structure identity and
number of end groups in each polymer molecule limited to relatively low
MW for sensitivity reasons 5,000 - 10,000 is typical MW range Can be
high with some detections types ©2002, Dr. Allen D. Hunter,
Youngstown State University Department of ChemistryChemistry 5861 -
Polymer Chemistry 9 ¾ ¾ C) radioactive labeling of end groups
fluorescent labeling of end groups
C. Sometimes this information comes out “free” during polymer structural
studies

iii) Weaknesses

A. does not give MW distribution information

B. need to know information about the structure
1. identity and number of end groups in each polymer molecule
c. limited to relatively low MW for sensitivity reasons
1. 5,000 - 10,000 is typical MW range
2. Can be high with some detections types - radioactive labeling of end
groups and fluorescent labeling of end groups