Polymer Properties

Exercise 1
 Structure

Draw the different stereoregular

polymer structures that can be
obtained.
 1a)
n CH2 CH CH3 CH2 CH
CH3
n

Stereoregularity of PP:

n n
isotaktinen PP syndiotaktinen PP
 1b)

CH3
CH2 C(CH3)2 CH2 C
CH3
n

No stereoregularity differences in polymer.

 1c)
CH3

CH CH CH CH2
n

H H
H CH2
C C
CH2 C C n
CH
CH H
n
CH3
CH3
cis trans

Also Syndiotactic

Also Isotactic
 1d)
CH3
CH3 CH CH C2H5 CH CH
C2H5
n

C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5

n n n

C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5

n n n
 Avarage molecular weights
Equations for number average and weight average molecular weights as well as polydispersity index are defined as
follows:

Mn 
 nM i i

 w i

n i n i
PD 
Mw
 wM  nM 2 Mn
Mw  i i
 i i

w i n M i i

where Mi molecular weight of molecules i

ni number of molecules with molecular weight i
wi mass of the molecules with molecular weight i
 2
A sample of polystyrene is
composed of a series of fractions of Table 1. PS fractions.
different sized molecules (total Fraction weight fraction Molecular weight
    [g/mol]
mass 10 g).
a) Calculate the number average A 0.130 11000

and weight average molecular B 0.300 14000

weights of this sample as well C 0.400 17000
as the PDI. D 0.170 21000
b) How would adding styrene
oligomer change the average
molecular weights? Added
amount is 5wt.% of polymer
mass and M=1000g/mol.
 2a)
• Determine the number of moles in each fraction. Assume that
the sample is 10 g in the beginning. Number of moles of the
fraction is ni = wi / Mi.
fractio wi Mi ni
n [g] [g/mol] [mmol]
A 1.30 11000 0.118
B 3.00 14000 0.214
C 4.00 17000 0.235
D 1.70 21000 0.0810
       
  wi = 10.0 g   ni = 0.648 mmol
 2a)
• Number average molecular weight:

Mn 
 nMi i

 w
i

10.0 g
 15400 mol
g

n i ni 0.648mmol

• Weight average molecular weight:

Mw 
 wM
i i

(1.3 11000  3.0 14000  4.0 17000  1.7  21000) g  mol
g
 16000 mol
g

w i 10.0 g

• Polydispersity index:
g
M w 16000 mol
PD   g
 1.04
M n 15400 mol
 2b)
• When 5.0 wt-% of styrene oligomer (fraction E) is added, the
total mass and number of moles increase as follow:
fraction wi Mi ni
[g] [g/mol] [mmol]
A 1.30 11000 0.118
B 3.00 14000 0.214
C 4.00 17000 0.235
D 1.70 21000 0.0810
E 0.50 1000 0.50
  wi = 10.5 g   ni = 1.10 mmol
 2b)
• number average molecular weight

Mn 
 nM
i i

10.5 g
 9150 mol
g

n i 1.10mmol

• weight average molecular weight

M 
 w M  (1.3 11000  3.0 14000  4.0 17000  1.7  21000  0.5 1000) g 
i i
g
mol
 15300 mol
g

  w
w
i 10.5 g

• Polydispersity index
 
g
M w 15300 mol
PD   g
 1, 67
Mn 9150 mol
 3 Viscosity
 t
• relative viscosity: r  
0 t0
  0 t  t 0
sp  
• Relative viscosity increment (or specific viscosity): 0 t0
sp
• Reduced viscosity (or viscosity number): red 
c
ln r
•  Inherent viscosity: inh 
c
 
• Mark-Houwink equation:     k  M va

• Intrinsic viscosity [] can be defined:

 sp   ln r 
    limc0    
  lim c 0  
 c   c 
 3)
• Viscosity of atactic polystyrene was measured in dilute
solutions and the results are presented in table 2.
• Determine the viscosity average molecular weight for the
sample . Mark-Houwink constants are k = 0.00848 ml/g and a
= 0.748.
Table 2. Efflux times for polystyrene samples. Solvent toluene. T =25°C.

Polystyrene concentration efflux time

[mg/ml] [t/s]
0 110.0
5.0 123.5
10.0 138.0
15.0 153.6
20.0 170.2
25.0 187.9
 3)
• Calculate the required viscosity parameters:
c efflux time r sp inh red
[mg/ml] [t/s]
= t/t0 = (t-t0)/t0 =ln( )/c = sp/c
r

0 110.0        
5.0 123.5 1.123 0.123 0.0232 0.0246
10.0 138.0 1.255 0.255 0.0227 0.0255
15.0 153.6 1.396 0.396 0.0222 0.0264
20.0 170.2 1.547 0.547 0.0218 0.0274
25.0 187.9 1.708 0.708 0.0214 0.0283

• Draw inh and red as function of concentration.

 • [] is obtained from the plot from the
3) crossing of y-axis:
  sp 
 
  lim c 0    0.0237 ml/mg =23.7 ml/g
 c 
ln r
    limc0  
 = 0.0236 ml/mg = 23.6 ml/g
 c 
• and the average from these is [] =
23.65 ml/g.
• Viscosity average molecular weight
from Mark-Houwink equation:

 
    k  M va  M va 
k
1
1  ml  0.748
23.65
    a  g 
 Mv       40205
 k   0.00848 ml 
 g 
Note! Due to empirical coefficients k ja a.  
the equation gives the molecular weight
without unit. In literature k = 0.007…0.01 g
M v  40000
and a = 0.69…0.78  accuracy of the mol
calculation is not particularly good.
 4) Light scattering
• Both weight average molecular weight Mw and second virial
coefficient A2 can be determined from graph when Kc/R(q) is plotted
as a function of concentration:
Kc 1
  2 A2 c
R ( ) M w

• 1/Mw is the cross point on y-axis and A2 is half of the linear

coefficient.
2
2  8 m 
3

2 2 2
 1, 4199   6, 297  10 
2 2 no2  dn   g  12 mol  m
2
K 4     1, 633 10
N A  dc  1
6, 023 10 mol  (6328 10 m)
23 10 4
g2
 5,E-06

4) 4,E-06

Kc/R mol/g
3,E-06
3 -1
c (g / m ) R( ) (m ) Kc / R( ) y = 5,29E-10x + 3,20E-06
5,034E+02 2,390E-04 3,440E-06 2,E-06 2
R = 9,77E-01
1,007E+03 4,400E-04 3,737E-06
1,510E+03 6,060E-04 4,071E-06 1,E-06
2,014E+03 7,900E-04 4,163E-06
2,517E+03 9,020E-04 4,558E-06 0,E+00
0 500 1000 1500 2000 2500
c / g/m3

• From the plot:

1 -6 mol g
= 3,20 10  M w  313000
Mw g mol

• And second virial coefficient:

mol  m3 mol  m 3
2 A2  5, 29 1010  A2  2, 64  10 10

g2 g2