Chapter 2.

Molecular Weight and Polymer Solutions

POLYMER CHEMISTRY
2.1 Number average and weight average molecular weight

2.2 Polymer solutions

2.3 Measurement of number average molecular weight

2.4 Measurement of weight average molecular weight

2.5 Viscometry

2.6 Molecular weight distribution
2.1 Number Average and Weight Average Molecular Weight


A. The molecular weight of polymers


a. Some natural polymer (monodisperse) :
All polymer molecules have same molecular weights.

b. Synthetic polymers (polydisperse) :
The molecular weights of polymers are distributed

c. Mechanical properties are influenced by molecular weight
much lower molecular weight ; poor mechanical property
much higher molecular weight ; too tough to process
optimum molecular weight ; 105 -106 for vinyl polymer
15,000 - 20,000 for polar functional group containing polymer (polyamide)

POLYMER CHEMISTRY
B. Determination of molecular weight



a. Absolute method :
mass spectrometry
colligative property
end group analysis
light scattering
ultracentrifugation.

b. Relative method : solution viscosity

c. Fractionation method : GPC

POLYMER CHEMISTRY
C. Definition of average molecular weight


a. number average molecular weight ( M
n
)

M
n
=

(colligative property and end group analysis)


b. weight average molecular weight ( M
w
)


M
w
=

(light scattering)

E
i i
EN
i

M N
EW
i

POLYMER CHEMISTRY
EW
i
M
i



c. z average molecular weight ( M
Z
)

M
Z
=

(ultracentrifugation)

d. general equation of average molecular weight :

M =

( a=0 , M
n
a=1 , M
w
a=2 , M
z
)

e. M
z
> M
w
> M
n



EN
i
M
i
3

EN
i
M
i
a+1

EN
i
M
i
a

EN
i
M
i
2

POLYMER CHEMISTRY
C. Definition of average molecular weight


polydispersity index (PI) = M
w
/ M
n
1



POLYMER CHEMISTRY
D. Polydispersity index : width of distribution
E. Example of molecular weight calculation



a. 9 moles, molecular weight (M
w
) = 30,000

5 moles, molecular weight ( M
w
) = 50,000

M
n
=
9 mol + 5 mol
(9 mol x 30,000 g/mol) + (5 mol x 50,000 g/mol)
= 37,000 g/mol
M
w
=
9 mol(30,000 g/mol) + 5 mol(50,000 g/mol)
9 mol(30,000 g/mol)
2
+ 5 mol(50,000 g/mol)
2

= 40,000 g/mol
POLYMER CHEMISTRY



b. 9 grams, molecular weight ( M
w
) = 30,000

5 grams, molecular weight ( M
w
) = 50,000

E. Example of molecular weight calculation
= 35,000 g/mol
M
n
=
9 g + 5 g
(9 g/30,000 g/mol) + (5 g/50,000 g/mol)
M
w
=
(9 g/30,000 g/mol) + (5 g/50,000 g/mol)
9 g + 5 g
= 37,000 g/mol
POLYMER CHEMISTRY
2.2 Polymer Solutions


A. Process of polymer dissolution : two step


first step : the solvent diffuses into polymer masses to make
a swollen polymer gel


second step : swollen polymer gel breaks up to solution



POLYMER CHEMISTRY
B. Thermodynamics of solubility :
Gibb's free energy relationship


AG = AH - TAS


G < 0 : spontaneously dissolve
T and S are always positive for dissolving process.
Conditions to be negative G,
H must be negative or smaller than TS.



POLYMER CHEMISTRY
2.2 Polymer Solutions


C. Solubility parameter :

AH
mix
=V
mix
[(

)
1/2
-( )
1/2
]
2
|
1
|
2







1
,
2
= volume fraction
E
1
/V
1
, E
2
/V
2
= cohesive energy densities

1
,

2
= solubility parameter


1,

2
= ( )
1/2


AH
mix
= V
mix
(
1

2
)
2
|
1
|
2

AE =AH
vap
- RT


1
=( )
1/2


if
1
=
2
, then H
mix
= 0





V
1

AE
1

V
2

AE
2

V
AH
vap
- RT
V
AE
POLYMER CHEMISTRY

D. Small's and Hoy's G parameter

a. Small(designated G derived from Heat of vaporization, Table 2.1)

=

( d : density , M : molecular weight of unit )

ex) polystyrene
= = 9.0

b. Hoy(designated G based on vapor pressure measurement, Table 2.1)

=


ex) polystyrene :

=

dEG
M
M
104
1.05(133+28+735)
dEG
M
M
104
1.05[131.5+85.99+6(117.1)]
= 9.3
POLYMER CHEMISTRY
E. Hydrodynamic volume of polymer molecules in solution.
to be depended on followings
a. polymer-polymer interaction
b. solvent-solvent interaction
c. polymer-solvent interaction
d. polymer structure ( branched or not )
e. brownian motion
r = end-to-end distance
s = radius of gyration

Figure 2.1 Coil molecular shape
The greater the value of , the better
the solvent
= 1, 'ideal' statistical coil.

r
2
=r
o
2
o
2
s
2
=

s
o
2
o
2

o =
(r
2
)
1/2

(r
o
2
)
1/2

F. theta() temperature and theta() solvent

The lowest temperature at which =1 : theta() temperature blink
The solvent satisfied this condition : theta() solvent point
G. Flory-Fox equation :
The relationship among hydrodynamic volumes,
intrinsic viscosity and molecular weight

[] : intrinsic viscosity
M : average molecular weight
: Flory constant (31024/mol)
r : end-to-end distance

[] =
|(r
2
)
3/2

M
POLYMER CHEMISTRY
2.2 Polymer Solutions
H. Mark-Howink-Sakurada equation

: The relationship between intrinsic viscosity and molecular weight

[] : intrinsic viscosity
K , a : constant for specific polymer and solvent
M : average molecular weight


I. Important properties of polymer solution : solution viscosity

a. paint spraying and brushing

b. fiber spinning

[] =KM
a

POLYMER CHEMISTRY
2.2 Polymer Solutions
2.3 Measurement of Number Average Molecular Weight

2.3.1 End-group Analysis


A. Molecular weight limitation up to 50,000
B. End-group must have detectable species

a. vinyl polymer : -CH=CH2
b. ester polymer : -COOH, -OH
c. amide and urethane polymer : -NH2, -NCO
d. radioactive isotopes or UV, IR, NMR detectable functional group
POLYMER CHEMISTRY
M
n
=
2 x 1000 x sample wt
meq COOH +meq OH
C.
D. 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

E. High solution viscosity and low solubility : Mn = 5,000 10,000
POLYMER CHEMISTRY
2.3 Measurement of Number Average Molecular Weight
FIGURE 2.2 Schematic representation of a membrane osmometer.
2.3.2 Membrane Osmometry

A. According to van't Hoff equation



limitation of : 50,0002,000,000
The major error arises from low-molecular-weight species diffusing
through the membrane.

(
c
t
)
C=0
=
M
n

RT
+A
2
C
FIGURE 2.3 Automatic membrane osmometer [Courtesy of Wescan Instruments, Inc.]
t/c
M
n

RT
C
Slope = A
2

FIGURE 2.4. Plot of reduced osmotic pressure (t/c) versus concentration (c).
POLYMER CHEMISTRY
2.3.3 Cryoscopy and Ebulliometry

A. Freezing-point depression (Cryoscopy)





AT
f
: freezing-point depression,
C : the concentration in grams per cubic centimeter
R : gas constant
T : freezing point
AH
f
: the latent heats of fusion
A2 : second virial coefficient
(
C
AT
f

)
C=0
=
AH
f
M
n

RT
2

+A
2
C
POLYMER CHEMISTRY
B. Boiling-point elevation (Ebulliometry)





AT
b
: boiling point elevation
AH
v
: the latent heats of vaporization


We use thermistor to major temperature. (110-4)
limitation of M
n
: below 20,000

(
C
AT
b

)
C=0
=
AH
v
M
n

RT
2

+A
2
C
POLYMER CHEMISTRY
2.3.3 Cryoscopy and Ebulliometry
2.3.4 Vapor Pressure Osmometry

The measuring vapor pressure difference of solvent and solution drops.


: the heat of vaporization per gram of solvent
m : molality


limitation of M
n
: below 25,000
Calibration curve is needed to obtain molecular weight of polymer sample
Standard material : Benzil

AT = (
100
RT
2

)m
POLYMER CHEMISTRY
2.3.5 Mass spectrometry

A. Conventional mass spectrometer for low molecular-weight compound
energy of electron beam : 8 -13 electron volts (eV)
POLYMER CHEMISTRY
B. Modified mass spectrometer for synthetic polymer


a. matrix-assisted laser desorption ionization mass spectrometry
(MALDI-MS)

b. matrix-assisted laser desorption ionization time-of-flight
(MALDI-TOF)

c. soft ionization
sampling : polymers are imbedded by UV laser absorbable organic
compound containing Na and K.

d. are calculated by using mass spectra.

e. The price of this mass is much more than conventional mass.

f. Up to = 400,000 for monodisperse polymers.



POLYMER CHEMISTRY
POLYMER CHEMISTRY
FIGURE 2.5. MALDI mass spectrum of low-molecular-weight poly(methyl methacrylate).
2.3.6 Refractive Index Measurement


A. The linear relationship between refractive index and 1/M
n
.

B. The measurement of solution refractive index by refractometer.

C. This method is for low molecular weight polymers.

D. The advantage of the method is simplicity.



POLYMER CHEMISTRY
2.4 Measurement of Weight Average Molecular Weight

2.4.1 Light Scattering

A. The intensity of scattered light or turbidity() is depend on following factors

a. size

b. concentration

c. polarizability

d. refractive index

e. angle

f. solvent and solute interaction
POLYMER CHEMISTRY
g. wavelength of the incident light
g. wavelength of the incident light









C : concentration
n
o
: refractive index of the solvent
: wavelength of the incident light
N
o
: Avogadro's number
dn/dc : specific refractive increment
P(u) : function of the angle,
A2 : second virial coefficient
Zimm plot (after Bruno Zimm) : double extrapolation of concentration
and angle to zero (Fig 2.6)



t = HcM
W

32t
3
H =

4
N
o

N
o
2
(dn/dc)
2

t
Hc
=
MP(u)
1
+ 2A
2
C
POLYMER CHEMISTRY
FIGURE 2.6. Zimm plot of light-scattering data.
sin
2
u/2 + kc
t
Hc
M
w

1
C=0
Experimental
Extrapolated
FUNCTIONAL POLYMERS LAB POLYMER CHEMISTRY
B. Light source
High pressure mercury lamp and laser light.
C. Limitation of molecular weight( ) : 104107
FUNCTIONAL POLYMERS LAB POLYMER CHEMISTRY
2.4.1 Light Scattering
FIGURE 2.7.
Schematic of a laser
light-scattering photometer.
2.4.2 Ultracentrifugation



A. This technique is used

a. for protein rather than synthetic polymers.

b. for determination of M
z



B. Principles : under the centrifugal field, size of molecules are
distributed perpendicularly axis of rotation.

Distribution process is called sedimentation.

FUNCTIONAL POLYMERS LAB POLYMER CHEMISTRY

2.5 Viscometry

A. IUPAC suggested the terminology of solution viscosities as following.
Relative viscosity :
q : solution viscosity
q
o
: solvent viscosity
t : flow time of solution
t
o
: flow time of solvent

Specific viscosity :



Reduced viscosity :


Inherent viscosity :


Intrinsic viscosity :

q
rel
=
q
o

q
=
t
o

t
q
rel
- 1 q
sp
=
q
o

q - q
o

=
t
o

t - t
o

=
c
q
rel
=
c
q
sp

=
c
q
rel
- 1
q
inh
=
c
I n q
rel

[q] = (
c
q
sp

)
c=o
=(
inh
)C = 0 POLYMER CHEMISTRY
FIGURE 2.8. Capillary viscometers : (A) Ubbelohde, and (B) Cannon-Fenske.
FUNCTIONAL POLYMERS LAB POLYMER CHEMISTRY
B. Mark-Houwink-Sakurada equation



[] = KM
a


log[] = logK + alogM
v

(K, a : viscosity-Molecular weight constant, table2.3)



M
v
is closer to M
w
than M
n




M
w


> M
v
> M
n

POLYMER CHEMISTRY
TABLE 2.3. Representative Viscosity-Molecular Weight Constants
a

Polymer

Polystyrene
(atactic)
c

Polyethylene
(low pressure)
Poly(vinyl chloride)

Polybutadiene
98% cis-1,4, 2% 1,2
97% trans-1,4, 3% 1,2
Polyacrylonitrile

Poly(methyl methacrylate-co-
styrene)
30-70 mol%
71-29 mol%
Poly(ethylene terephthalate)
Nylon 66
Solvent

Cyclohexane
Cyclihexane
Benzene
Decalin

Benzyl alcohol
Cyclohexanone

Toluene
Toluene
DMF
g
DMF


1-Chlorobutane
1-Chlorobutane
M-Cresol
M-Cresol
Temperature,

o
C
35
d
50
25
135

155.4
d
20

30
30
25
25


30
30
25
25
Molecular Weight
Range 10
-4
8-42
e

4-137
e

3-61
f

3-100
e


4-35
e

7-13
f


5-50
f

5-16
f

5-27
e

3-100
f



5-55
e

4.18-81
e

0.04-1.2
f

1.4-5
f

K
b
10
3

80
26.9
9.52
67.7

156
13.7

30.5
29.4
16.6
39.2

17.6
24.9
0.77
240
a
b

0.50
0.599
0.74
0.67

0.50
1.0

0.725
0.753
0.81
0.75


0.67
0.63
0.95
0.61
a
Value taken from Ref. 4e.
b
See text for explanation of these constants.
c
Atactic defined in Chapter 3.
d
u temperature.
e
Weight average.
f
Number average.
g
N,N-dimethylformamide.
POLYMER CHEMISTRY
2.6 Molecular Weight Distribution


2.6.1 Gel Permeation Chromatography (GPC)

A. GPC or SEC (size exclusion chromatography)

a. GPC method is modified column chromatography.

b. Packing material: Poly(styrene-co-divinylbezene),
glass or silica bead swollen and porous surface.

c. Detector : RI, UV, IR detector, light scattering detector

d. Pumping and fraction collector system for elution.

e. By using standard (monodisperse polystyrene), we can obtain M
n
, M
w
.

POLYMER CHEMISTRY
FIGURE 2.9. Schematic representation of a gel permeation chromatograph.
POLYMER CHEMISTRY
POLYMER CHEMISTRY
FIGURE 2.10. Typical gel permeation chromatogram. Dotted lines represent volume counts.
Elution volume (V
r
) (counts)
Baseline
Detector
response
POLYMER CHEMISTRY
FIGURE 2.11. Universal calibration for gel permeation chromatography. THF, tetrahydrofuran.

Log([]M)
10
9

10
8

10
7

10
6

10
5

18 20 22 24 26 28 30
+
A

A
Polystyrene (linear)
Polystyrene (comb)
Polystyrene (star)
Heterograft copolyner
Poly (methyl methacrylate)
Poly (vinyl chloride)
Styrene-methyl methacrylate graft copolymer
Poly (phenyl siloxane) (ladder)
Polybutadiene
+
+
+
+
A
A
A
A





A
A
A
A
Elution volume ()5 ml counts, THF solvent)
POLYMER CHEMISTRY
FIGURE 2.12. Typical semilogarithmic calibration plot of molecular weight versus retention volume.
Retention volume (V
r
) (counts)
10
6

10
5

10
4

10
3

M
o
l
e
c
u
l
a
r

w
e
i
g
h
t

(
M
)

B. Universal calibration method





to be combined Mark-Houwink-Sakurada
equation
[]
1
M
1
= []
2
M
2

logM
2
= (
1 + a
2

1
)log(

K
2

K
1

) + (
1 + a
2

1 + a
1

)logM
1

POLYMER CHEMISTRY
2.6.2 Fractional Solution





Soxhlet-type extraction by using mixed solvent.

Reverse GPC : from low molecular weight fraction
to high molecular weight fraction

Inert beads are coated by polymer sample.
POLYMER CHEMISTRY
2.6.3 Fractional Precipitation




Dilute polymer solution is precipitated by variable non-solvent mixture.

Precipitate is decanted or filtered

Reverse fractional solution : from high molecular weight fraction to
low molecular fraction

POLYMER CHEMISTRY
2.6.4. Thin-layer Chromatography (TLC)




Alumina- or silica gel coated plate.

Low cost and simplicity.

Preliminary screening of polymer samples or
monitoring polymerization processes.

POLYMER CHEMISTRY