Polymer Molar Masses and Sizes
Polymer Solutions: J ustification 1.
Polymer characterization techniques are solution based techniques.
Molecular Weight Characterization: Probe Single Molecules
Gel Permeation Chromatography (GPC): M
n
, M
w
, M
z
Low Angle Light Scattering (LALS): M
w
Vapor Phase Osmometry and Membrane Osmometry: M
n
Intrinsic Viscosity: M
v
Microstructure:
Tacticity (stereo isomerism), Geometrical Isomerism,
Regio isomerism.
Degree of Branching
Copolymer Composition and Distribution:
Polymer Solution: J ustification 2.
In some applications, polymers are either in solution or in contact
with liquids.
Coatings
Paints (emulsions)
Contact Lenses (gels)
Polymer for drug delivery (blood)
Fiber spinning (high performance PE and Kevlar
TD
fibers)
Separation Membranes
Diapers...
Thermodynamics of Polymer Solutions
Mixing of two components 1 (solvent) and 2 (polymer) is
spontaneous if G
mix
< 0
Gibbs Free Energy of Mixing under Isothermal Conditions (cst T)
G
mix
=G
1+2
- (G
1
+G
2
) and G =H - TS
G
mix
= H
mix
- T S
mix
Enthalpic Contribution is a
measure of how much the
polymer and the solvent like
or dislike each other.
Entropic Contribution is a
measure of the disorder
generated by the mixing
process. (#of configurations)
Thermodynamics of Polymer Solutions
Free Energy of Mixing Polymer and Solvent
G
mix
=H
mix
- T S
mix
S
mix
>0 S
mix
= - (n
1
+n
2
)R (x
1
lnx
1
+x
2
lnx
2
) Ideal Soln.
S
mix
= - (n
1
+n
2
)R (x
1
lnv
1
+x
2
lnv
2
) Polymer Soln.
mix
<0 specific interactions (hydrogen bonding, dipoles)
mix
0 athermal solutions
mix
>0 dispersive interactions (regular solutions)
mix
=RTn
1
v
2
(: the Flory-Huggins interaction parameter)
Thermodynamics of Polymer Solutions
Hildebrand & Scott (Regular solution theory): Dispersive Int.
H
mix
= V
MIX
[
1
2
]
2
v
1
v
2
V
MIX
solution volume
v
i
volume fraction of component i
i
solubility parameter
Solubility Parameter
= (E
VAP
/ V
M
)
1/2
measures the strength of intermolecular interactions in a pure
liquid (cohesive energy density).
Solubility Parameters (SP pp. 67-68)
0.86 8.8 Xylene 1.06 9.1 Polstyrene
1.00 23.5 Water
0.79 14.5 Methanol 1.28 13.6 Cellulose triacetate
1.03 10 1,4-Dioxane 1.24 13.6 Nylon 66
0.79 9.9 Acetone 1.20 9.9 Poly(ethylene oxide)
0.88 9.2 Benzene 1.39 9.6 Poly(vinylchloride)
0.87 8.9 Toluene 1.19 9.5 Polymethylmethacrylate
1.59 8.6 Carbon tetrachloride 1.01 8.4 Polybutadiene
0.78 8.2 Cyclohexane 0.85 7.9 Polyethylene
6.6 n-decane 0.92 7.9 Polyisobutene
5.1 Difluorodichloromethane 2.0 6.2 Polytetrafluoroethylene
Solvent
Polymer
Determination of Solubility Parameters
Small Molecules (solvent):
Measure H
VAP
Calculate U
VAP
=H
VAP
RT
Polymers:
Swelling of cross-linked polymer
Intrinsic viscosity []
Group contribution method
= ( / M
ru
) G
i
and M
ru
are the density and the repeat unit molar mass for
the polymer. G
i
is a group contribution to the solubility
parameter.
Average Molar Masses
M
n
: Number Average Molar Mass
M
w
: Weight Average Molar Mass
M
z
: Z-Average Molar Mass
N
i
: Number of molecules of mass M
i
w
i
: Total mass of all molecules having each molar mass M
i
M
n
N
i
M
i
i
N
i
i
M
w
N
i
M
i
2
i
N
i
M
i
i
w
i
M
i
i
w
i
i
M
z
N
i
M
i
3
i
N
i
M
i
2
i
w
i
M
i
2
i
w
i
M
i
i
Number Average Molar Mass
Techniques that measure M
n
are based on counting the molecules
regardless of shape and molar mass of the polymer molecules.
Three general methods for the determination of M
n
End-group Analysis
Colligative Properties
Transport Properties
End-group Analysis
Ability to detect end-groups (nature of end-group and chain
length)
A-priori knowledge of the number of end-group per chain
Use of NMR, IR, Titration
Limited to Step-Growth Polymers and M
n
< 15,000 to 20,000 g/mol
Number Average Molar Mass
Colligative Properties (Properties of Collections)
Classical 19th century techniques developed for small molecules.
Properties of dilute solutions of unknown solute in known solvent
expressed in terms of the physical properties of the solvent and the number
of molecules of solute.
These techniques include:
Lowering of Vapor Pressure of Solvent
Elevation of Boiling Point of Solvent
Depression of Melting Temperature of Solvent (see book)
Osmotic Pressure of Solution
Concept of Osmotic Pressure
Solvent
Polymer
(solvent in solution) =(solvent pure) +RT ln a
S
<(solvent pure)
Net flow of solvent into polymer solution:
Concept of Osmotic Pressure =
Osmotic Pressure Measurements
P
atm
+P
atm
c
2
RT
1
M
n
+
v
2
2
V
1
1
2
_
,
c
2
+...c
2
2
+...
1
]
1
Net Flow Equilibrium
Example of Osmotic Pressure Data
c
RT
1
M
n
+ A
2
c + A
3
c
2
+
1
]
1
/c
c
If the second virial coefficient
A
2
=0 (
F-H
=1/2) then the
solution is in the Theta State
lower limit: M
n
ca. 15,000 g/mol
c
Number Average Molecular Mass Determination
Using Transport Methods: Vapor Phase Osmometry
Technique applicable for M
n
between 50 and 20,000 g/mol
R
K*c
1
M
n
_
,
1+
1
2
2
c
1
]
1
2
K* M
n
lim
c0
R
c
_
,
T between two thermistors arises because the
difference in vapor pressure between solution and
solvent leads to condensation of solvent vapor on
solution drop. T leads to R in the bridge.
Low Angle Light Scattering:
Determination of the Weight Average Molar Mass
Light scattering arises because of fluctuations in the local index of
refraction within the polymer solution because of the presence of
polymer chains (which have a different refractive index than the
solvent). Interferences between waves scattered by different part of a
polymer chain lead to an intensity I which varies with scattering angle
(). I() provides information about chain dimensions and molar mass.
Detector
S
Polymer Dimensions :
Mean Squared End to End Distance
Mean Squared End to End Distance
r : End to End Vector
<r>: Mean End to End Vector =0
<r
2
>: Mean Squared End to End Distance
<r
2
>=C
inf
n l
2
C
inf
: Characteristic Ratio (chain stiffness)
n : Number of Chemical Bonds
l : Length of Bonds (1.54 A for C-C)
Radius of Gyration R
g
=<R
g
2
>
1/2
R
g
2
=(1/6) <r
2
>
Light Scattering from Polymer Solutions
Measurements of the scattering intensity as a function of
polymer concentration and scattering angle at fixed
temperature allows for the determination of the mean square
radius of gyration of the polymer chains in solution, the
weight average molar mass and the second virial coefficient
A
2
(A
2
is proportional to 1/2 - ) for the polymer solution.
K' 1+ cos
2
( )
c
R
1
M
W
+ 2A
2
c
_
,
1+
1
3
4
_
,
2
R
g
2
sin
2
2
_
,
K'
2
2
n
0
2
dn dc ( )
2
4
N
a
V I
r I
R
0
2
Rayleigh Ratio
Zimm Plot
Intrinsic Viscosity and The Viscosity Average Molecular Mass
When a polymer is dissolved in a liquid, the dimension of the
polymer coils depends on the solution concentration and on the
nature and strength of interactions between the solvent and the
polymer. Since the size of the polymer molecule is much larger
than that of the solvent, a drastic increase in the solvent viscosity is
observed when even a small amount of polymer is dissolved in.
Staudinger showed that the relative increase in solution viscosity
can be related to some molar mass average of the polymer chains
(viscosity average).
When using a capillary viscometer, the ratio (t/t
0
) of the flow
time t of a polymer solution of concentration c to that t
0
of the
pure solvent is proportional to the ratio of their viscosity (/
0
) if
temperature is kept constant and the density does not change
with polymer concentration in solution.
Experimental Viscometry
r
=(t / t
0
) =( /
0
) relative viscosity
sp
=
r
-1 =(t - t
0
) / t
0
specific viscosity
red
=
sp
/ c
2
reduced viscosity
inh
=(1 / c
2
) Ln (
r
) inherent viscosity
[] intrinsic viscosity
red
=[] +k []
2
c k is a constant
inh
=[] +k []
2
c k is a constant
Ubbelohde
Viscometer
[]
Viscosity Molecular Weight - Intrinsic Viscosity Relation
ln []
ln M
[] =K M
v
a
Mark-Houwink-
Sakkurada Equation
K and a are constants
that depend on
solvent/polymer pair
and temperature.
a =0.5 Theta Solvent
at temperature
a =0.8 Good Solvent
Gel Permeation Chromatography:
Determination of the Molecular Mass Distribution Curve
Gel Permeation Chromatography
( Size Exclusion Chromatography)
Liquid Chromatography:
Separation of Components of a mixture in a solution phase
through interactions with a stationary phase.
Gel:
The stationary phase is composed of crosslinked porous
polystyrene beads through which and around which the
solution flows
Permeation (Steric Exclusion):
Principle by which the separation of molecules of different
sizes is taking place when the molecules attempt to go
through the pores of the stationary gel phase.
GPC/SEC Principle
A dilute polymer solution is injected in the GPC column filled with
crosslinked polystyrene beads.
A sampler at the bottom of the column(s) gathers successive
aliquots of the solution flowing through the column. A variety of
detectors (IR, UV, RI, etc..) allow for the measurement of the
concentration (c
i
) of polymer in the solution eluting at a given time
or for a given elution volume (V
i
). Sometimes, light scattering or
viscometric detectors are also used, which allow for absolute
molecular weight determination.
Although the solution is injected rapidly in the column, all polymer
molecules do not elute at the same time or elution volume.
The larger the polymer molecules, the larger their hydrodymanic
volume, the fewer the pores they can penetrate, the faster they
travel, the sooner they elute (the lower the elution volume).
GPC Equipment Diagram
Larger molecules
travel less and elute
sooner
Analysis of the GPC Trace
Hydrodynamic Volume: 2.5 N
a
V
H
=[] M and V
H
= <R
g
2
>
3/2
where S
2
is the mean squared radius of gyration, is the physical
molecular characteristic leading to separation of the different
molecules (not the molar mass). is a universal constant.
Calibration curve:
A calibration curve for a given
column is prepared by measuring
the elution volume of a series of
monodisperse polymer standards
of known molecular mass. The
calibration curve allows to relate
V
el
to M. However such curves
are not unique and are only valid
when the investigated polymer is
identical to the narrow molar mass
standard.
from Fundamentals of Polymer Science
by P.C. Painter, M.M. Coleman
from Fundamentals of Polymer Science
by P.C. Painter, M.M. Coleman
Absolute Calibration for
the Determination of
Absolute Molecular Mass
Distribution
Need to measure [] to get
absolute Molecular Mass
Polymers having the same
hydrodynamic volume (V
H
) (i.e.
the same [] M elute at the same
time (same elution volume))
Practical Aspects of the Analysis
Intensity or signal h
i
is proportional
to the concentration c
i
of polymer in
the aliquot of volume V
elut
.
c
i
=N
i
M
i
/ N
a
V
elut
w
i
=h
i
/ h
i
(mass fraction)
The elution (retention) volume V
elut
i
is related to the molecular mass M
i
.
Note V
elut
i+1
- V
elut
i
=V
elu
.
M
N
=1 / ( (w
i
/ M
i
)
M
W
= w
i
M
i
M
V
=( N
i
M
i
a+1
/ N
i
M
i
)
1/a
