̅𝑛 ,

like to synthesize polystyrene with a number-average molecular weight, 𝑀

of 90 000 g/mol?
(3 points)

3.2 Vinyl acetate is polymerized in a free-radical reaction. The initial monomer

CHEM-E2100 Polymer synthesis concentration is 1.0 mol/dm3 and after 1 hour of polymerization its concentration
Exercise 3: Chain polymerization II: Chain transfer; ATRP is 0.85 mol/dm3. To adjust the molecular weight, chloroform is used as chain
transfer agent. The initial chloroform concentration is 0.01 mol/dm 3 and after 1

This exercise set will be discussed and solved in class on Thursday 1st of October at hour the chloroform concentration is 0.007 mol/dm3. Calculate the chain transfer

8:15-9:45 (lecture room KE1, Kemistintie 1) or at 12:00-14:00 in Microsoft Teams. To constant, C, for the polymerization reaction. (2 points)

get exercise points you need to return carefully written solutions before Monday 5th of
October at 10:15. You should return your solutions using the submission box in
MyCourses (as a single PDF file). 3.3 ATRP (Atom Transfer Radical Polymerization) of styrene ([M]0 = 5.0 M) was
carried out at 110 °C. 1-phenylethyl bromide (c = 0.050 M) was used as initiator
and CuBr (c = 0.050 M) as catalyst in the presence of 4,4’di(5-nonyl)-2,2’-
bipyrine (c = 0.20 M) as the ligand. The number-average molecular weight at
3.1 Styrene is polymerized in ethylbenzene at 60 °C using di-tert-butyl peroxide
72 % conversion was 7250 g/mol.
(DTBP) as initiator. The initial styrene and di-tert-butyl concentrations are 1.0
a) Write the ATRP reactions for this polymerization reaction.
mol/dm3 and 0.01 mol/dm3, respectively. The rate of polymerization, RP, is
b) Compare the experimental number-average molecular weight to the
1.5·10-7 mol/(dm3·s) and the rate of initiation, Ri, is 4.0·10-11 mol/(dm3·s). Chain
theoretical one expected for this polymerization.
transfer to the solvent can be neglected and no termination through
c) Compare the polydispersity index (𝑋̅𝑤 / 𝑋̅𝑛 ) of the synthesized polymer to
disproportionation is expected. The chain transfer constants are: CM = 8.0·10-5,
the theoretical polydispersity index of this polymerization. How would the
CI = 3.2·10-4, CP = 1.9·10-4 and CS = 21.
polydispersity index change if more CuBr would be added to the reaction
a) Calculate fkd and the initial kinetic chain length, ν.
mixture?
̅𝑛 , of the synthesized
b) Determine the number-average molecular weight, 𝑀
(3 points)
polymer if no chain transfer agents are used.
c) To avoid high molecular weights, chain transfer agents, such as butanethiol,
can be employed. What butanethiol concentration is needed if you would
1/2
3.4 Styrene ([M] = 8 M, constant throughout the whole polymerization) was
polymerized in bulk at 60 °C using benzoyl peroxide as initiator. The following
experimental data was obtained from the polymerization:

Table 1. Experimental data for bulk polymerization of styrene.

Rp (mol/(dm3·s) ̅𝒏
𝑿

5.00·10-6 8350

1.00·10-5 5550

2.00·10-5 3330

5.00·10-5 1510

1.00·10-4 592

1.50·10-4 358

a) Calculate 𝑘𝑝 /√𝑘𝑡 , CM, and fkd when it is experimentally demonstrated that

the termination does not occur through disproportionation and that the rate
of polymerization obeys the following equation:

𝑚𝑜𝑙
𝑅𝑃 = 4.0 ∙ 10−4 √ ∙ √[𝐼]
𝑑𝑚3 ∙ 𝑠 2

HINT: Use the equation 3-20 to 3-23, 3-32 and 3-108 in Odian and plot
1/Xn vs. RP to determine the asked values.
b) Based on the 1/Xn vs. RP plot, why is the chain transfer to initiator
substantial?
c) Determine CI in the case of chain transfer to initiator.
HINT: Plot [1/Xn-CM]/RP vs. RP to determine CI.
(4 points)

2/2