MSE 470 / MAE 455

Polymers and Composites

Topic #7 Molecular Weight and Size

• How is the molecular weight of a polymer specified?

• What is a molecular weight distribution?

• How are number average & weight average MW calculated?

• What are the size and shape of a polymer chain?

• How are the size and shape of a polymer chain modeled?

• What experimental methods characterize polymers?

 Addition Polymers - Vinyls

Semicrystalline
Semicrystalline
Amorphous
Amorphous

Molecular Weight Calculation

Degree of Polymerization (DP) = (MW of polymer chain) / (MW of mer)
Example: What is DP for a sample of polypropylene with MW = 300,000 g/mole?
Introduction
◼ What is the shape of a polymer
molecule?

◼ What molecular parameters

can be used to specify the
“size” of a polymer molecule?
Introduction
◼ What is the shape of a polymer
molecule?

◼ What molecular parameters

can be used to specify the
“size” of a polymer molecule?
 Molecular Weight Distribution
Number average molecular weight
Mn = Xi Mi
Xi = number fraction of molecules in the i th interval of
particular molecular weight in an MW distribution
Mi = specific MW of molecules in the i th interval
.
.
.
Weight average molecular weight
Mn = Wi Mi
Wi = weight fraction of molecules in the i th interval of
particular molecular weight in an MW distribution
Mi = specific MW of molecules in the i th interval
.
.
.
Polydispersity (Index of polydispersity)
PD = polydispersity = Mw / Mn > 1 (Monodisperse PD = 1)
Molecular Weight Distribution
Example - Molecular Weight Calculation
Example - Molecular Weight Calculation
Molecular Size and Dimensions
Molecular Size and Dimensions
Size Model – Root-Mean-Square End-to-End Distance
Gel Permeation Chromatography (GPC)
 FIGURE 2.10. Typical gel permeation chromatogram. Dotted lines
represent volume “counts.”

Detector Baseline
response

Elution volume (Vr) (counts)

molecular weight and PDI
Molecular Weight Characterization
 Measurement of Number Average Molecular Weight

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
 Measurement of Number Average Molecular Weight
2 x 1000 x sample wt
C. Mn =
meq COOH + meq OH

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
Measurement of Weight Average Molecular Weight

Light Scattering

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

factors

a. size

b. concentration

c. polarizability

d. refractive index

e. angle

f. solvent and solute interaction

g. wavelength of the incident light
 g. wavelength of the incident light
 = HcMW

32 No2(dn/dc)2
H=
3 4No
1
Hc = + 2A2C
 MP()

C : concentration
no: refractive index of the solvent
λ : wavelength of the incident light
No : Avogadro's number
dn/dc : specific refractive increment
P() : function of the angle,θ
A2 : second virial coefficient
Zimm plot (after Bruno Zimm) : double extrapolation of concentration
and angle to zero (Fig 2.6)
 FIGURE 2.6. Zimm plot of light-scattering data.

Hc

C=0

Experimental
1 Extrapolated
Mw
sin2/2 + kc
Light Scattering
B. Light source
High pressure mercury lamp and laser light.
C. Limitation of molecular weight( ) : 104～107

FIGURE 2.7.
Schematic of a laser
light-scattering
photometer.
Mass Spectrometry
◼ Molecular weight can be obtained from a very
small sample.
◼ It does not involve the absorption or emission
of light.
◼ A beam of high-energy electrons breaks the
molecule apart.
◼ The masses of the fragments and their relative
abundance reveal information about the
structure of the molecule.

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Separation of Ions

◼ Only the cations are deflected by the magnetic

field.
◼ Amount of deflection depends on m/z.
◼ The detector signal is proportional to the
number of ions hitting it.
◼ By varying the magnetic field, ions of all
masses are collected and counted.

23
Mass Spectrometer

24
The Mass Spectrum
Masses are graphed or tabulated according to
their relative abundance.

25
Matrix-Assisted Laser Desorption/Ionization (MALDI)

◼ Analyte is mixed with UV-absorbing matrix

❑ ~10,000:1 matrix:analyte ratio
❑ Analyte does not need to absorb laser
◼ A drop of this liquid is dried on a target
❑ Analyte incorporated into matrix crystals
◼ Spot is irradiated by a laser pulse
❑ Irradiated region sublimes, taking analyte with it
❑ Matrix is often promoted to the excited state
❑ Charges exchange between matrix and analyte in the
plume (very fast <100 nsec)
◼ Ions are accelerated toward the detector
MALDI Example

(ACTH 18-37+H)+ (ACTH 7-38+H)+

(Ubiq+2H)2+

(Ubiq+H)+
(Ins+H)+
 Summary

◼ A polymer is characterized by its molecular weight

distribution in terms of Mw and Mn.
◼ What is a molecular weight distribution?
◼ How are number average Mn & weight average MW
calculated?
◼ Polymers are experimentally characterized by: end
group analysis; colligative chemical potential light
scattering and solution viscosity