CHEM-E2130 Polymer Properties

Exercise 1: Stereoregular polymers, average d)

molecular weights
Exercise 1.2
Exercise 1.1
Draw the different stereoregular polymer structures (different tacticities) A sample of polystyrene (10 g total mass) is composed of a series of
that can be obtained from the following repeating units. NOTE: Cis-trans fractions of different sized molecules
isomers are also possible, in particular for unsaturated carbons
a) Calculate the number average- and weight average molecular
weights of this sample, as well as the PDI.

b) How would adding styrene oligomer change the average

a)
molecular weights? The added amount is 5 %wt of polymer mass
and M=1000g/mol.

Table 1. PS fractions.
Fraction weight fraction Molecular weight
[g/mol]
b) A 0.130 11000
B 0.300 14000
C 0.400 17000
D 0.170 21000

c)
Exercise 1.3* Kc 1
  2 A2 c
R( ) M w
The viscosity of atactic polystyrene was measured in dilute solutions and where R() Rayleigh ratio, Mw weight average molecular weight, c particle
the results are presented in Table 2. concentration (g/m3), A2 second virial coefficient and K is a function of the
refractive index:
Determine the reduced and inherent viscosities and plot them as a function
of concentration. Use the obtained intrinsic viscosity value to calculate the
2 2 no2  dn 
2

viscosity average molecular weight ( M v ) for the sample. Mark-Houwink K  

N A 4  dc 
constants are k = 0.00848 ml/g and a = 0.748.

Table 2. Efflux times for polystyrene samples. where no is the refractive index of the pure solvent, NA is Avagadro’s
Solvent toluene, T = 25°C. number (6,0231023 mol-1),  wavelength, dn/dc specific refractive
Polystyrene concentration efflux time increment of the dilute polymer solution.
[mg/ml] [t/s]
0 110.0 For cellulose acetate, the Rayleigh ratio R() in dioxane obtained from
5.0 123.5 LALLS measurement at different concentrations is:
10.0 138.0
15.0 153.6 c (g/m3) R() (m-1)
20.0 170.2 5.034E+02 2.390E-04
25.0 187.9 1.007E+03 4.400E-04
1.510E+03 6.060E-04
Exercise 1.4* 2.014E+03 7.900E-04
2.517E+03 9.020E-04
Low-Angle Laser Light-Scattering = LALLS (2o-10o) can be used to
determine the molecular weight of polymer particles even from very dilute The refractive index for dioxane is no = 1.4199, cellulose acetate solution
solutions using the Debye equation: dn/dc is 6.29710-8 m3/g and the wavelength is  = 6328 Å. Plot Kc/RΘ
as a function of concentration (g/m3). From the resulting curve, calculate
the weight average molecular weight (y-axis intercept = 1/Mw) and the Exercise 1.6
second virial coefficient (2A2 = line gradient).
The following measurements have been obtained for a polymer solution at
25oC:
Kc 1
  2 A2 c c (g/dL) h (cm of solvent)
R( ) M w 0,32
0,66
0,70
1,82
1,00 3,10
1,40 5,44
1,90 9,30
Exercise 1.5*
Density of the solvent is 0.85 g/cm3.
Polymers A and B are monodisperse polystyrenes. The molecular weight
of Polymer A is three times the molecular weight of Polymer B. Polymer
a) Plot π/(RTc) as a function of concentration c.
C is polydisperse PS with Mw = 2.0105 g/mol. A mixture containing 25g
of Polymer A, 50g of Polymer B and 25g of Polymer C was measured with
b) Determine the average molecular weight (y-intercept = 1/Mw) for
light scattering, and molecular weight obtained was 112,500 g/mol. With
the polymer and the second virial coefficient (line gradient).
osmotic pressure, the molecular weight was determined to be 60,000
g/mol. Estimate the number average molecular weight Mn of the polymer
C.    gh

Hint: Convert all units to meters (for height), g/m3 (for

Hint: Consider what type of molecular weight values are given by osmotic
concentration) and kg/m3 (for density)
pressure and light scattering measurements (consult the slides)

Remember to check the unit of temperature also!

The only equations you will need are:

Mn 
n M
i i

w
i
and Mw 
w M  n M
i i i i
2

n i n
i w n M
i i i

...and some knowledge of algebra