MOLECULAR WEIGHT OF

POLYMER
Ch2
Key Point
1. Understanding of polymer molecular weight (MW)
2. MW distribution and average concept
3. Number- & weight average molecular weight , Mn & Mw
4. Calculation of average MW and polydispersity index
5. Polymer molecule in solution
6. Techniques of MW measurement
7. Solution viscosity and the relationship to MW
 Importance of MW and MWD
✓ Extremely important variable because it relates directly to a
polymer’s physical properties

In general, Higher the molecular weight, the tougher the polymer

lower molecular weight polymer has poor mechanical property
if molecular weight is too high, the processing becomes difficult

✓ Optimum MW depends on chemical structure of the polymer and

the applications intended

* Typical MW value for commercial polymers ;

105 ~ 106 for vinyl polymer
104 ~ range for polar functional group containing polymer
(e.g. 15,000~20,000 for Nylon)
 Molecular Weight Distribution
Molecular Weight Distribution
▪ Some natural polymer is monodisperse : all polymer molecules
have same molecular weights.

▪ Synthetic polymers are polydisperse : The molecular weights of

polymers are distributed 대부분polydoperse

Formation of macromolecules during polymerization results in

distribution of chain lengths and molecular weights.
: A given polymer sample can be considered as a mixture of
the polymer chains of different lengths.
(The breadth of distribution depends on the
specific conditions of polymerization)

It is necessary to define average MW

1. Number Average and Weight Average
Molecular Weight (Mn, Mw)
Number Average (Mn) and Weight Average(Mw)
Molecular Weight
General equation for molecular weight average:

a=1 Mn , a=2 Mw , a=3 Mz

• Z-average Molecular Weight (z stands for centrifuge. German

zentrifuge)
Polydispersity index (PDI)
: measure of the breath of molecular weight distribution

Mw / Mn (≥ 1)

For most polymers

Mw/Mn: 1.5–2.5

For monodisperse polymer:

Mw/Mn = 1 해
.
M
 Determination of Molecular Weight

• Primary (absolute) method : osmometry (Mn), end group analysis

(Mn), light scattering (Mw), ultracentrifugation (Mz), mass
spectrometry.
최적
• Secondary (relative) method : gel-permeation chromatography
(GPC) or SEC (Mn, Mw, MWD), viscometry (Mv)
2. POLYMER SOLUTIONS & SOLUBILITY
 General Rules for Polymer Solubility
비슷한 것끼리 녹임
• Likes dissolve likes: e.g. PVA/H2O, PS/toluene
• In a given solvent at a particular temperature, the solubility of a
polymer will decrease with increasing molecular weight
• Crosslinking eliminate solubility
• Crystallinity acts like physical crosslinking, require strong solvent or
heat to overcome the crystalline bonding force
• The rate of dissolution decrease with increasing molecular weight

* LCST behavior

How does one choose a solvent ?

 Thermodynamics of Solubility

Entropy of Mixing

Enthalpy of Mixing

Gibbs free energy of mixing

ㅇ
이혼합 : SX
 Prediction of Solubility

(Hildebrandt) Solubility Parameter, d

dE = dH - RT

Since polymer is non-volatile, d of polymer is determined indirectly

1) by group-contribution methods
(by Small, Hoy, van Krevelen)
2) by comparing the swelling of crosslinked polymer, experimentally
팽창
DHydrodynamic volume of polymer molecule in solution

r = end-to-end distance
s = radius of gyration (Rg)

Kr
< Bz ) =

6
=
Np
(

How large is a polymer Blob α=1 at theta(θ) temperature

Free-jointed-chain model
Molecular size in solution
Once a polymer-solvent system has been selected, another consideration is how the polymer
molecules behave in that solvent.
In the standpoint of molecular weight determination, the size of polymer in solution, or
hydrodynamic volume is important. The hydrodynamic volume will depend on several factors
including interaction between solvent and polymer molecules, conformational effect arising
from the polarity and steric bulk of substituent group, restricted rotation, and so on.
Molecular size is generally expressed in terms of the mean square average end-to-end
distance, r2, or mean square average radius of gyration about the center of gravity, s2. The
average shape of coiled molecule is assumed spherical.

It is convenient to express r or s in terms of two factors: an unperturbed dimension (r0 or

s0) and the expansion factor (a).

Unperturbed dimension refers to the size of the macromolecule exclusive of solvent effect.
It arise from a combination of free rotation, intramolecular steric and polar interactions. The
expansion factor, on the other hand, arises from the interaction between solvent and polymer.
a will be greater than unity in a “good” solvent, The greater the value of alpha, the ‘better”
the solvent. For a special case, where a equal 1, the polymer assume its unperturbed
dimensions and behave as a “ideal” statistical coil.
 “Poor” “Good”

The effect of solvent power and temperature on a polymer molecule in

solution
Flory-Fox equation

[η] : intrinsic viscosity

M : average molecular weight “Mark-Houwink-Sakurada

f : Flory constant (3×1024/mol) (MHS) equation”
r : end-to-end distance
3. Measurement of Mn (number average MW)

1. End-group Analysis
2. Membrane Osmometry
3. Cryoscopy and Ebulliometry Colligative method
4. Vapor Pressure Osmometry
5. Mass Spectrometry (MALDI-TOF MS)
End-group Analysis

1. chemical titration, 2. element analysis, 3. measurement of activity of a

(radioactive)-tagged end group, 4. spectroscopic analysis such as UV, or
NMR techniques.

Practice Problem : Mn by ‘end-group titration’ method

A sample (3 g) of linear polyester (one chain end is carboxylic acid)
required titration with 20 mL 0.1N KOH to reach a phenolphthalein
end-point. Calculate Mn (g/mol) of the polymer:

Answer:
Practice Problem: Proton NMR (1H NMR) is used to attempt to quantify the
molecular weight of a poly(ethylene oxide) molecule with methoxy end group at
one terminal. If the integration of the methyl protons relative to the methylene
protons gave a ratio of 1:20, what can you say about the molecular weight of this
polymer?

CH3-O-[CH2CH2-O-]n-H

-CH2 CH3
Colligative Methods : Using colligative properties of solution,
that depend on the number (mole) of solute molecules in a solution,
and not on the nature of the chemical species present

A Comparison of Colligative Properties of 1%(w/v) Solution

of Polystyrene (PS) of MW 20,000 in Benzene
Property Value
Vapor pressure lowering 0.004 mmHg
Boiling point elevation 0.0013 oC
Freezing point depression 0.0025 oC
Osmotic pressure 15 cm solvent head
 막 삼투압측정
Membrane Osmometry

Osmotic pressure

p = r gh
Van’t Hoff equation
Problem
At 20 oC, the osmotic pressure of a polycarbonate was measured
in chlorobenzene with the following results:

Concentration (g/L) 1.95 2.93 3.91 5.86

Osmotic pressure
0.20 0.36 0.53 0.98
(cm chlorobenzene)

[solvent density = 1.10 g/cm3; polymer density = 1.20 g/cm3.]

Estimate: (a) polymer molecular weight, Mn

(b) second virial coefficient A2
MALDI-TOF-MS
Polymer Analysis by MALDI-Tof MS

Mn = 2079,
Mw = 2232,
polydispersity
(PDI = Mw/Mn)
= 1.07

Figure. Polystyrene 2000 MALDI micro MX spectrum

4. Measurement of MW (weight average MW)
: by Light-Scattering
Zimm Method
5. Viscometry and Mv (viscosity average MW)

Capillary Viscometer

점도
-
분자량에 의존
Determination of Intrinsic Viscosity [h]

“Huggins equation”
“Mark-Houwink-Sakurada (MHS) equation”
: relate intrinsic viscosity to Mv, viscosity average mol. wt.

(1)

log[h] = log K + a log M

(2)

Mw > Mv > Mn
6. Molecular Weight Distribution (MWD)
: Gel Permeation Chromatography
Fractionation by hydrodynamic volume of polymer molecule

sipe

exdusion
GPC chromatogram
Calibration Plot (Universal)
Major Methods for MW Measurements

Membrane osmometry Ave MW Upper limit

Method Measure parameter measured (g/mol)
Osmotic pressure of polymer solvent Mn 5x10⁴
Membrane Osmotic pressure of polymer
osmometry solution Mn 5x104
Light scattering (LS)
Intensity of light scattered
Light scattering byofdilute
Intensity polymer by
light scattered solutions Mw 1x10⁸
(LS) dilute solution Mw 1x108
Gel permeation chromatography (GPC)
Gel permeation Elution volume of the
Elution volume of thepolymer
chromatography polymer solution
solution through
through a a GPC column packed
with
(GPC)porous microparticles Mn, Mw
GPC column packed 108
1 x with Mn, Mw 1x108
porous microparticles
Viscometry
Viscometry
Flow time of polymerFlow time of
solution polymerasolution
through capillary Mv 1 x 10 8
through a capillary Mv 1x108