POLYMER

CHEMISTRY
Molecular weight of polymer
 polymers

monodisperse polydisperse

nucleic all synthetic

protein
acid polymers
Degree of polymerization (X) = number of monomers
in the chain
M = M0X
M0 = the molecular weight of the monomer and M =
the molecular weight of the polymer
 MOLECULAR WEIGHT
• Molecular weight, M : Mass of a mole of chains.

low M

high M

• Polymers can have various lengths depending on the

number of repeating units.
• During the polymerization process not all chains in a polymer
grow to the same length, so there is a 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. 7
MOLECULAR WEIGHT DISTRIBUTION

M n  xi M i
M w  wi M i

__
M
__w = the weight average molecular weight
Mn = the number average molecular weight
Mi = mean (middle) molecular weight of size range i
xi = number fraction of chains in size range i
wi = weight fraction of chains in size range i
9
10
 Commercial grades of polystyrene
with a Mn of over 100,000 have
polydispersity index between 2 and 5,
while polyethylene synthesized in the
presence of a stereospecific catalyst
may have a PDI as high as 30. In
contrast, the PDI of some vinyl
polymers prepared by “living”
polymerization can be as low as 1.06.

Polydispersity index

= 2.0 for condensation polymers

must be  1. When it is = 1,
the CV = 0 which means that the
distribution is monodisperse
• Mechanical properties such as stiffness, strength,
viscoelasticity, toughness, and viscosity
• Resistance to heat

If molecular weight is too low, the transition temperatures and

the mechanical properties will generally be too low for the
polymer material to have any useful commercial applications.

For a polymer to be useful it must have transition temperatures

to waxes or liquids that are above room temperatures and it must
have mechanical properties sufficient to bear design loads.

much lower molecular weight ; poor mechanical property

much higher molecular weight ; too tough to process
 constant

molecular
weight

strength at infinite M average

strength molecular
weight
 Commercial
range

Tensile
strength

Impact
Polymer resistance
properties
Melt
viscosity

MW
Molecular weight determination

By end-group analysis,
eg., hydroxyl number, Bycolligativep
carboxyl equivalent, etc. roperties

By Gel By
viscometry By light
PermeationCh scattering
romato- method
method
graphy(GPC)
• Mn < 25,000 by vapor
pressure osmometry
• Mn = 50,000–2 million by
membrane osmometry
• Mn < 50,000 by end group
analysis, such as NMR for
C=C; titration for carboxylic
acid ending group of
polyester
• Mw = 10,000–10,000,000 by
light scattering
At present, the gel
permeation
chromatography (GPC)
technique has been
advanced to be able to
easily measure Mn, Mv, Mw
simultaneously and
calculate PDI using only
one sample
 MW
Method range, g/mol
1. Membrane osmometry 104-106
2. Ebullioscopy (boiling point elevation) <104
3. Cryoscopy (freezing point depression) <104
4. Isothermal distillation <104
5. Vapor Phase osmometry <105
6. End group analysis <105
7. Static light scattering 102-108
11. Solution viscosity 102-108
12. Gel Permeation Chromatography 102-107
 Boiling
point
elevation

By colligative Freezing
point
properties depression

Osmotic
pressure
 Boiling
point
elevation

At equilibrium,
the chemical
potential in the
solution will be
equal to the
chemical
potential in the approximation
pure solvent
 Freezing
point
depression
For an example, let’s consider
a solution of polystyrene in benzene.
For benzene  = 0.8787 g/cm3, Tb =
55C, and lvap = 104 cal/g. We assume a For measureable Tb
relatively concentrated solution of It should be :
c = 1 g/cm3 of a polymer with molecular • concentrated solution
weight MN = 20,000, Tb = ?? • low MW

Tb = 1.4 × 10−3 C very small

not sensitive
beyond the accuracy of most
temperature measuring equipment
 Osmotic
pressure For an example, let’s consider a solution
of polystyrene in benzene.
 = 0.8787 g/cm3, c = 1 g/cm3
MN = 20,000
R = 8.3143 × 107 ergs/K/mol
 = 1.24 × 104 dynes/cm2
This pressure will be measured by a
difference in heights of liquids in
columns,  = gh, thus h = ??

easily measurable quantity

osmotic pressure can, in principle, be used to determine

molecular weights in polymers with MN up to 2,000,000 g/mol
Membrane
osmometry

Y = a + bx
• membrane must be
permeable to solvent
and impermeable to • Therefore, polydisperse
polymer. This polymers probably
requirement limits the require MN greater
low-end applicability of than about 50,000
osmometry to MN of g/mol;
20,000 g/mol or more for monodisperse
polymers it might be
possible to go down to
20,000 g/mol
 Problems
The following are data
from osmotic pressure
measurements on a
solution of polyester in
chloroform at 20C. The
results are in terms of
cm of solvent. The
density of CHCl3 is 1.48
g/cm3. Plot /c versus c R = 8.3143 × 107 ergs/K/mol
and find MN g = 981 cm/sec2
800000
y = 7E+07x + 329928
700000
R² = 0.9999
600000
500000
400000
300000
0 0.002 0.004 0.006

intersep=32992
intersep=RT/M
RT= 24360020000
M= 738361.421
 Problems
Osmotic Osmotic Osmotic
c (g/L) pressure at pressure at pressure at
30.0C (atm) 41.6C (atm) 53.5C (atm)
2.7 0.00046 0.00052 0.00061
12.5 0.00210 0.00248 0.00293
17.0 0.00265 0.00343 0.00384
22.0 0.00323 0.00442 0.00543

Plot /c versus c and find MN

 By viscometry
method

The sp
relative
= [] + k′[]2c
c
viscosity

specific
viscosity

The plot of sp/c versus c :

gives a straight line, with
the intercept of [η]

The intrinsic viscosity also called the limiting viscosity number

 Mark-Houwink-Sakurada equation
k and a are characteristic of the particular
solvent/polymer combination
 Polymer-solvent
k x 103 mL/g a
system
PMMA-Acetone 7.70 0.70
PMMA-Benzene 5.20 0.76
PMMA-Toluene 7.0 0.71
Poly vinyl acetate-
10.2 0.72
Acetone
Poly vinyl acetate-
56.3 0.62
Benzene
Poly vinyl acetate-
41.5 0.62
Acetonitrile
Poly vinyl alcohol-
45.3 0.64
Water
Poly styrene-Benzene 10.6 0.735
Poly styrene-Toluene 11.0 0.725
 By end-group
Basic principles analysis
• The structures of the
end groups must be
different from that of
the bulk repeating units

• If the end groups can be

analyzed, the number of
polymer molecules may be can be determined
calculated using simple
stoichiometric relationships
HO-CH2-(CH2-CH2)n-CH2-OH
alcohol groups, which may be
analyzed by a reaction known
as esterification
analyzed by 1H NMR
Detection of concentrations
of end groups
 Spectroscopy : IR, NMR,
UV-Vis
 Elemental Analysis
 Radioactive or Isotopic
labels
• Calculation, integral per proton
• Calculation, number of repeating monomer units, n
• Calculation, Mn:
Mn = (FW end groups) + (FW repeating unit)(n)
Requirement for end group analysis
1. The method cannot be applied to branched
polymers.
2. In a linear polymer there are twice as many end
of the chain and groups as polymer molecules.
3. If having different end group, the number of
detected end group is average molecular weight.
4. End group analysis could be applied for
polymerization mechanism identified
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
• radioactive labeling of end groups
• fluorescent labeling of end groups
 By light
scattering
method red sunsets

blue sky and clouds

When light interacts with matter, it causes charges to polarize

The oscillating charges

radiate light.
How much the charges move,
and hence how much light radiates,
depends upon the matter’s polarizability.
 Index of refraction (n)
The polarizability of a material is
directly related to its index of
refraction (n).
The index of refraction is a measure of
the velocity of light in a material.
2
For solutes, the polarizability is  dn 
I scattered  
expressed as the specific  dc 
refractive index increment, dn/dc.
How light scattering measures M

2
 dn 
I scattered  Mc 
 dc 
 scattering
at low
concentrations

2
Iex (k) 1 2n dn  cMV
I0

NA   dc  r
2 2 P(k)1  2A2 Mc  
 Light Scattering Data Processing
Kc /R q

Slope=2A2

Intercept=1/M

Concentration, c
MW
distribution
Gel permeation
Chromatography (GPC)

• Polymer fractions are

separated on the basis of
particle size
• Smaller particles permeate
the gel preferentially
• The highest molecular weight
fractions are eluted first
• Polystyrene gel with pore
sizes 1 to 106 nm acts as a
stationary phase.
 The separation mechanism here
relies solely on the size of the
polymer molecules in solution,
rather than any chemical
interactions between particles and
the stationary phase

The mixture of different sized polymer

molecules is eluted in a solvent
through a column of porous particles.
The smaller molecules can enter the
pores, whereas the larger molecules
move out
 Molecular weight (g/mol)

Retention time (min)

Schematic of a basic gel permeation chromatograph
Problems
Table 1
If the degree of
polymerization is
477, which of the
polymers in the
Table 1 is this
material?
Data pengukuran viskositas menggunakan
viskometer Ostwald :
Konsentrasi (g/cm3) x 102 Waktu alir (detik)
0.0000 170
0.03535 178
0.05152 182
0.06484 185
0.100 194
0.200 219
0.400 275
Buat kurva sp/c vs c, dan hitung M jika
[] = 3,4 x 10-3 M0,8 cm3/g
165
160 y = 6647.5x + 132.14
155 R² = 0.9924
[] = 3.4x10-3 M0.8
150
log [] = log 0.0034 + 0.8 log M
145 log 132.1 = -2.4685 + 0.8 log M
140 0.8 log M = 4.5894
log M = 5.7368
135 M = 5.4548x105
130
0 0.001 0.002 0.003 0.004 0.005