4.2 Styrene is polymerized in bulk at 60 °C.

The emulsion system (case 2 behavior:

𝑛̅ = 0.5) contains 3.6×1013 polymer particles per ml, the monomer concentration
is 5.0 mol/dm3 and the rate of initiation is 1.1×1014 dm-3/s. The propagation rate
constant is 145 dm3/(mol×s).
a) Calculate the rate of termination rt, of a polymer chain. (0.5 points)
CHEM-E2100 Polymer synthesis b) What is the number-average molecular weight of the polymer produced?
Exercise 4: Chain polymerization III: Emulsion polymerization, (1 points)

polymerization mechanisms and ionic polymerization c) Give at least one advantage and at least one disadvantage of emulsion
polymerization compared to bulk and solution polymerization. (0.5 points)

This exercise set will be discussed and solved in class on Thursday 8th of October at
8:15-9:45 (lecture room KE2, Kemistintie 1) or at 12:00-14:00 in Microsoft Teams. To
4.3 Sodium naphthalene (1.0×10-3 mol) is dissolved in tetrahydrofuran, after which
get exercise points you need to return carefully written solutions before Monday 12th
styrene ([M]0 = 2.2 mol) is injected into the system. The final volume of the
of October at 10:15. You can return your solutions using the submission box in
solution is 1 L. You can assume that the injection of styrene results in
MyCourses (as a single PDF file).
instantaneous homogeneous mixing. After 1800 s, half of the monomer is
polymerized.
a) Calculate the propagation rate constant, kp. (1.5 points)
4.1 Radical polymerization can also be conducted in an emulsion. Compare the
b) Calculate the degree of polymerization, 𝑋̅𝑛 , after 1800 s and 3600 s. (1.5
emulsion and bulk polymerization of styrene at 60 °C. The emulsion
points)
polymerization (𝑛̅ = 0.50) contains 1.0×1015 polymer particles/ml. In both
HINT: Initiation occurs via electron transfer (Odian chapter 5-3a-2) → no
polymerizations, [M] = 4.0 mol/dm3, Ri = 5.00·1015 radicals/(dm3×s) and kp =
chain transfer or termination, chain propagation from both ends.
221 dm3/(mol×s). The rate constant for termination is kt = 6.02×107 dm3/(mol×s).
The termination occurs by combination.
a) Calculate the rate of polymerization, Rp, for both polymerizations) (1.5
points)
b) Calculate the number-average degree of polymerization, 𝑋̅𝑛 , for both
polymerizations. (1.5 points)

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4.4 Styrene is polymerized in tetrahydrofuran at 25 °C using butyllithium as
initiator. Chain transfer and termination do not occur. Initial monomer and
initiator concentrations are [M]0 = 2.0 mol/dm3 respective [BuLi] = 3.2·10-5
mol/dm3, and kp = 550 dm3/(mol·s).
a) Calculate the number-degree of polymerization, 𝑋̅𝑛 , and number-average
̅𝑛 , and polydispersity index when the conversion is 80
molecular weight, 𝑀
%. (1 point)
HINT: Molecular weight distribution follows the Poisson distribution.
b) How long does it take to reach conversions of 0 %, 25 %, 50 % and 75 %?
(1 point)
HINT: To calculate the time it takes to reach different conversions, you
need to integrate the equation for the polymerization rate.
c) Calculate the rate of polymerization, Rp, for the above-mentioned
conversions (0 %, 25 %, 50 % and 75 %). (1 point)
d) Calculate the number-average degree of polymerization, 𝑋̅𝑛 for the above-
mentioned conversions (0 %, 25 %, 50 % and 75 %). (1 point)

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