MTT656 Polymer Characterization and Analysis

3
3.1

( )
( )

3.1

3.1



()

3
( M n )
=

Mn

( M W )
=

MW

N i M i
N i

Ni M i
N i M i
2

(Mv)

Mv

N i M i 1 a

N i M i

1/ a

.. (.)

 MTT656 Polymer Characterization and Analysis

a = Mark-Houwink

~ 0.5 0.8

N =
M =
(Mn)
(Mw) (Mv)
Mn Mw

Mv Mw Mn ( 3.2)
3
( 3.2)

3.2 (molecular weight distribution curve)

Mw Mn polydispersity index (PDI)
3.2 Mw Mn PDI
Mw Mn PDI 1
PDI 1
( monodisperse polymer)
living polymerization
PDI
gel permeation chromatography (GPC) (standard)
PDI 1

PDI 1

.. (.)

 MTT656 Polymer Characterization and Analysis

3.2

1. End group analysis (absolute method)
2. Osmometry (absolute method)
3. Viscometry
4. Gel permeation Chromatography
5. Light scattering (absolute method)

3.1
3.1
Method
Type
Molar mass range
(g/mol)

Average value

Membrane osmometry

104 105

Mn

End group analysis

< 104

Mn

Light scattering

103 107

Mw

Viscometry

102 -107

Mv

Size exclusion
chromatography (SEC) or
GPC

102 -107

Mn, Mv, Mw, PDI

A = Absolute method (polymer Mw is directly calculated from the experimental data, without additional
information on the chemical structure of the polymer
E = Equivalent method (chemical structure of polymer must be known for a calculation of polymer Mw)
R = Reference method (data must be calibrated with samples of known Mw)

3.2.1 End group analysis

end group analysis (sensitivity)
end group
end group analysis 50,000 (

low Mw polymer Mw 10,000)

.. (.)

 MTT656 Polymer Characterization and Analysis

1.1 COOH disproportionation
hydrogenation
1.2 (elemental analysis)
1.3 activity radioactive end group (14C)
1.4 chromophore UV spectroscopy

end group analysis

( branch branch
)
end group
H2N R COOH end group
HOOC R COOH 1 2
end group analysis
(initiation) (termination)
unsaturated polymer dicarboxylic acid diol polyester
COOH OH COOH/OH
2 end group
2

HOOC R COOH + HO R OH

HO R O C R C O R O C R COOH

HO C O R O C R C O R O C R COOH

HO R O - C R C O R O C R C O R OH
carboxylic acid
phenophthaline 2 3
( KOH) KOH

.. (.)

 MTT656 Polymer Characterization and Analysis

(
end group )
hydroxyl (OH) titrate
acetic anhydride OH anhydride
R OH + CH3 C O C CH3

R O C CH3 + HO C CH3
KOH
( 2 ( ) KOH
COOH free acetic acid
( acetic anhydride)
OH
COOH OH

COOH + OH
2

X (

)
Mn

( COOH + OH) / 2

.. (.)

 MTT656 Polymer Characterization and Analysis

(M.P. Stevens, 1990)

1. What is the DP of a sample of polyester prepared from 4 hydro oxybenzoic acid if the acid
number, determined with standard KOH solution is 11.2 ?

1. Acid number = (mg) base 1 g polymer

2. 4 hydroxybenzoic acid

.. (.)

 MTT656 Polymer Characterization and Analysis

2. A 0.5 g sample of unsaturated polymer resin was reacted with excess acetic anhydride. Titration
of the reaction mixture with 0.0102 M KOH required 8.17 mL to reach the end point. What is the
number average molecular weight of the polyester? Would this method be suitable for determining any
polyester ? Explain ( M.P. Stevens, 1990)
Note: M n

assumption
OH polyester diol excess
polyester COOH OH COOH

.. (.)

 MTT656 Polymer Characterization and Analysis

3.2.2 Osmometry
(colligative properties)
( 3.3)

3.3

(membrane)
equilibrium (
osmotic pressure )
Osmotic pressure ( )

gh

= g / cm 3
= 9.8 m / s 2
g
h = ( cm )

Van' t Haff

/c =

A2 c A2 c 2 ....
RT
Mn

Vant Haff

.. (.)

 MTT656 Polymer Characterization and Analysis

=

C C 0

R
A2

RT
+ A2 C
Mn

=
=
=

( g / dm 3 )
0.082 dm3 . atm / mol. K (gas constant)
Second varial coefficient interaction

= (Kelvin)

M n
plot / c c ( 3.4)

3.4
( L.H.Sperling, 1991, Wiley Interscience)
extrapolat e y Van' t Hoff equation
ideal solution dilute solution
(interaction)
A2 ( y RT / M n )
(good solvent) (coil)
( d > 1)
12 A2
A2 = (1 / 2 12)
2

1 = molar volume
= specific volume polymer

.. (.)

 MTT656 Polymer Characterization and Analysis

3.5 /c (c) PMMA 3

(a) toluene, (b) acetone and (c) acetonitrile
theta () solvent
(- condition ) ( acetonitrile 3.5) A2
solvent 3.1
3.1 solvent

()
()
n-haptane
(-1)

Biphenyl
125

Benzene/methanol (52/48)
25

Cyclohexane
34
nd
( J. Brandrup and E.H. Immergut, Eds., Polymer Handbook, 2 ed., Wiley-Interscience, NY, 1975)

Osmometry 50,000 2,000,000

() 50,000 ()

.. (.)

 MTT656 Polymer Characterization and Analysis

3.2.3 Viscometry
colligative ( end group analysis osmometry) light scattering
(LS) (absolute) (
)

(viscometry)
viscometry intrinsic viscosity
(MV)



MarkHouwink

kMV

= intrinsic viscosity
k a MarkHouwink
k a
k a

a 0.5 1
(flexible) a 0.5 0.9
flexibility conformation linear chain
warm like ( cellulose polyelectrolyte) a 1
a 1 conformation rod a
1.7 2.0 ( H. Pasch, B. Trathnigg,. HPLC of Polymers, Springer, 1999, p 15.)

3.2.3.1 k a
k a natural log (ln) MarkHouwink
ln

ln k + a ln M V

intrinsic viscosity M V
monodisperse polymer M n M W (
osmometry, LS) M V = M n = M W ( monodisperse)
intrinsic viscosity plot ln ln M V
3.6 a y ln k
.. (.)

 MTT656 Polymer Characterization and Analysis

3.6 logarithm Mw anionic

polymerization polydispersity index 1.06
30
() ( ) ()
[ L.H.Sperling, 1999]
PDI 1 (polydisperse polymer)
M V M n M W M W k a
M V M W M n ( polydispersity < 3 M W

M V %) k a
Polymer Handbook ( 3.2)
k a
Handbook M V
3.2 k

k x 103
( C)
a
-

30
33.7
0.715

139
21.5
0.67

25
51
0.59

20
5.5
0.73

30
22
0.65

25
39
0.58

34.5
84.6
0.50
(-solvent)

28
25.1
0.78
31.8
206
0.49
(-solvent)
J. Brandrup and E.H. Immergut, Eds., Polymer Handbook, 2 nd ed., Wiley-Interscience, NY, 1975
.. (.)

 MTT656 Polymer Characterization and Analysis

k a
SBR

k a k a

3.2.3.2 intrinsic viscosity M V
2
1. Huggins equation

sp
=
C

+ k ' 2C

=
sp = specific viscosity
k ' = Huggins coefficient
good solvent
k ' ~ 1/3
0.5 1 poor solvent

2. Kramer equation
ln rel
C

= - k ' ' 2 C

= relative viscosity
k ' ' = Kramer coefficient
k ' + k ' ' = 0.5
2 sp / rel plot
C /

ln rel
C
C

sp

.. (.)

 MTT656 Polymer Characterization and Analysis

2 Y ( intrinsic viscosity) k '

k ' '
sp rel
viscometer ( 3.7 )

3.7 Viscometer Oswald Ubbelohde

Capillary Viscometer
= At

( )
( 0 ) relative viscosity ( rel )
.. (.)

 MTT656 Polymer Characterization and Analysis

rel

rel

At
At 0 0

t0 0

rel

t
t0

Capillary
rel specific viscosity ( sp )
sp

r - 1

0
0

rel , sp
4 ( plot )

1-20 g / dm 3
M W 10-40 g / dm 3
M W 1-5 g / dm 3

.. (.)

 MTT656 Polymer Characterization and Analysis

Poisevilles equation
dV
dt

dV
dt
P

r
lc

Pr 4

8 lc

= volume of liquid flowing through the capillary/time ( cc / sec )

= hydrostatic pressure
= viscosity
= radius capillary
= length capillary

V
t

Pr 4
8 lc

=
P

gh

8 V lc
g hr 4

At

( kinetic energy pressure capillary

)

1. M W 20,000 flow time

Mark Houwink conformation
rod-like worm like coil
2. capillary flow time
M V
3. flow time
thermostat water bath
4.
flow time
membrane syringe viscometer

.. (.)

 MTT656 Polymer Characterization and Analysis

3.2.4 Gel Permeation Chromatography

Gel permeation Chromatography (GPC) Size Exclusion Chromatography (SEC)

random coil hydrodynamic
volume (assumption
)

random coil hydrodynamic volume

( hydrodynamic volume random coil)


GPC
Size Exclusion Chromatography (SEC)

3.8

detector UV
detector Reflective Index detector (RI)
( retention time ) GPC chromatogram
3.9

.. (.)

 MTT656 Polymer Characterization and Analysis

3.8 GPC
(F) (x-axis) retention time (tRt)
retention time GPC chromatogram
retention volume
TRt =

TRt
V Rt
F

=
=
=

V Rt
F

Retention Volume
Retention Volume
Flow rate column ml / min

1 ml / min GPC
chromatogram
polydispersity Index

(resolution)
resolution resolution
2 1 ( 3.9)
porous bead (high packing
.. (.)

 MTT656 Polymer Characterization and Analysis

density) separation efficiency bead

back pressure

3.9 GPC (a) resolution

(b) resolution separation efficiency (c) resolution selectivity
GPC Instrument
3.10 GPC
(solvent reservoir)
(solvent delivery system)
(injection port)

(detector)
(recorder)
(waste collector)

.. (.)

 MTT656 Polymer Characterization and Analysis

3.10 GPC
non
aqueous GPC ( ) THF
THF
GPC detector UV detector THF UV grade
chromophore
THF

0.1 % ( g / mol )

flow rate 1 ml / min (

resolution )
8 0.25
ml / min 4

(porous small beads)

(particle size bead

3-20 m )
crosslinked PS ( styreneDVB copolymer) DVB
crosslinking agent THF ( )

.. (.)

 MTT656 Polymer Characterization and Analysis

modified silica crosslink hydrophilic silica, crosslink polyhydroxy ehtylmethacylate
crosslinked PVA ( 3.3)
3.3 GPC

packing
Polymer Laboratories
PL gel
Waters
Styragel
Shodex
Asahipak GF HQ
Protein KW
Chitopak KQ

Styrene-divinylbenzene copolymer
Styrene-divinylbenzene copolymer
Highly crosslinked poly(vinyl alcohol) *
Silica *
Chitosan *

* (for aqueous SEC)

(packing bead)
(pore diameter) 10 - 107 (A0)
coil
25 60 cm 5 8 mm 1
efficiency resolution
separation efficiency
( column mixed bed
column porosity column )
1x102 1x106
2

1. Column size ( x )
2. Particle size 5 m ( particle size )

Detector
Detector 2
1. UV/visible spectrometer
A = l c
2. Differential Refractometer RI detector RI

.. (.)

 MTT656 Polymer Characterization and Analysis

(reference column)
detector RI detector

detector GPC retention time (
elution time) ( )
retention time retention volume flow rate

3.11 GPC
retention volume calibration curve
(standard) retention volume
column (flow rate, conc etc.) calibration
curve

.. (.)

 MTT656 Polymer Characterization and Analysis

3.12 GPC calibration curve

[ H. Pasch and B. Trathnigg, HPLC of Polymers, Springer, Berlin, 1999

polydispersity index 1 calibrate narrow Molecular weight
calibration

calibrate
hydrodynamic volume random coil
THF retention time
retention time calibration curve
M W

.. (.)

 MTT656 Polymer Characterization and Analysis

Universal calibration

calibration curve
Universal Calibration Curve M W VRt
3.13

3.13 Universal calibration curve

Universal Calibration Curve Hydrodynamic Volumn
M W
k a
2 viscometer detector detector GPC
retention time retention volume

samp M sample

std M s tan dad

.. (.)

 MTT656 Polymer Characterization and Analysis

std samp MarkHouwink

std

k M std

samp

k M samp samp

astd

1
log
log M samp =
1 a

samp

k std

+ 1 a std log M std

k

1 a

samp
samp

.. (.)

 MTT656 Polymer Characterization and Analysis

3.2.5 ( Light Scattering)

Light scattering weight averaged molecular weight
(
mercury lamp laser
LALLS)
(reflection)
(scattering) ( gas )
( I ) ( I ( 0) )
M W
Rayleigh ratio ( R( ) )

V
r

=
=

I ( ) r 2

R( )

I (0) V

Scattering Volume
detector sample cell

R( ) M W
Kc
R

1
M W PC

2 A2 C

K = refraction index [RI]

RI
A2 = Second varial coefficient (interaction)

random coil
A2 ( )
A2 ()
P( ) = Particle scattering function ( form factor)
P( ) =

Scattering intensity (finite angle)

Scattering intensity 0 0
=

R
R0

.. (.)

 MTT656 Polymer Characterization and Analysis

(00 20) P( ) = 1
Kc
R

1
MW

+ 2 A2 c

Low Angle Laser Light Scattering (LALLS) Static laser light scattering
laser
(
7 ) ( static light scattering) P( ) 1

Kc
R

1
MW

+ 2 A2 c

extrapolation

MW

LALLS radius of
gyration (multi-angle laser light scattering, MALLS)
radius of gyration

MALLS
MW
I R plot
Kc
sin 2 ( / 2) + k' c
R

2 3.14

.. (.)

 MTT656 Polymer Characterization and Analysis

3.14 Zimm plot

Zimm plot double extrapolate c = 0
= 0
Kc
R

1
+ 2 A2 c
MW P( )

Kc
R

1
MW

extrapolate ( C)
A2
(

Kc
)
R

.. (.)

 MTT656 Polymer Characterization and Analysis

( )
About Radius of gyration
R g 2 mean square distance gravity
random coil R g end-to-end distance ( r )
Rg

r2
6

r = coil conformation spheres,

rods
r 2 MW
r2 =

CM

C = factor

Schematic representation of a molecular coil. r = end-to-end distance,

s = radius of gyration, (r0)2 =Unpurturbed dimension (mean-square average)

= Expansion factor

.. (.)

 MTT656 Polymer Characterization and Analysis

Radius of gyration ( R g )
second varial coefficient ( A2 ) Zimm plot
optical constant (K/ R( ) ) (C) (K/ R( ) )
sin 2 ( / 2)
[
physical polymer science, L.H.Sperling, John Wiley & Sons, 1992, NY, p.88-94]

Introduction to

radius of gyration
1.

kc
(C) extrapolate c = 0 y
R

2. y sin 2 ( / 2) extrapolate
1
( double extrapolation
MW
Zimm plot) R g

second varial coefficient ( A2 )

3.

kc
1
sin 2 ( / 2)
2 3
R
MW

4. y 3 ( c ) y - intercept
Zimm plot double extrapolation

1
MW

( c 0

kc
R

1
MW

second varial coefficient ( A2 )

.. (.)