Exercise 3

Chain polymerization II:

Chain transfer; ATRP
01.10.2020
 General information
• I have graded your exercises (both Exercise 1 and 2). Please,
let me know if you have any questions.
• Overall, you all did a good job, but pay attention to the
following things in the upcoming exercises and the exam:
– Round of your answers according to the given values
– Give also the units for the answers
– If it is not explicitly stated in the exercise you can not assume that the
initiator or monomer concentration is constant over time
– Learn how to calculate M0
• Next week (8th of October), the exercise session will be in
KE2 (not in KE1 as usual)

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 Chain transfer

• Radical is transferred from the growing chain to another

molecule
k𝑡 𝑟
𝑀𝑛 ∙ +𝑋𝐴 𝑀𝑛 − 𝑋 + 𝐴 ∙

• Premature termination yields polymers with lower

molecular weight than expected
• Monomer consumption stays the same despite the chain
breaking

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 Effect of chain transfer

• Chain transfer will affect the number-average degree of

polymerization
1 𝑅𝑖 𝑆 𝐼
= + 𝐶𝑀 + 𝐶𝑆 + 𝐶𝐼
𝑋ത𝑛 2𝑅𝑝 𝑀 𝑀

– CM, CI and CP are chain transfer constants

– [M] = concentration of monomer
– [I] = concentration of initiator
– [S] = concentration of chain transfer agent
– Ri = rate of initiation
– Rp = rate of polymerization

Odian p. 239
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 Kinetic chain length, 

• Average number of monomer molecules

consumed per each radical, which initiates a
polymer chain
Rp Rp
v= =
Ri Rt

Odian p. 236
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 Hints, exercise 3.2

• The radical is transferred from the growing chain

to another molecule
k𝑡 𝑟
𝑀𝑛 ∙ +𝑋𝐴 𝑀𝑛 − 𝑋 + 𝐴 ∙

• Therefore, the rate of a chain-transfer reaction

can be given as
−𝑑[𝑋𝐴]
𝑅𝑡𝑟 = = 𝑘𝑡𝑟 𝑀 ∙ [𝑋𝐴]
𝑑𝑡
Odian p. 238
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 Hints, exercise 3.2

• The rate of polymerization is

−𝑑[𝑀]
𝑅𝑝 = = 𝑘𝑝 𝑀 ∙ [𝑀] Odian p. 207
𝑑𝑡

• Solve [M∙] from both equations

𝑘𝑡𝑟
• The chain transfer constant is C =
𝑘𝑝

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 Hints, exercise 3.3

• For ATRP reactions, the number-average

degree of polymerization is
𝑀 0 − [𝑀] 𝑝 𝑀 0
𝑋ത𝑛 = =
𝐼0 𝐼0

• The polydispersity index is

𝑋ത𝑤 1
𝑃𝐷𝐼 = =1+
𝑋ത𝑛 𝑋ത𝑛

𝑋ത𝑤 [𝐼]0 𝑘𝑝
𝑃𝐷𝐼 = =1+ , where D is the deactivating agent
𝑋ത𝑛 𝑘𝑑 [𝐷]

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 Hints, exercise 3.4

• Chain transfer will affect the number-average degree of

polymerization
1 𝑅𝑖 𝑆 𝐼
= + 𝐶𝑀 + 𝐶𝑆 + 𝐶𝐼
𝑋ത𝑛 2𝑅𝑝 𝑀 𝑀

• In this case, we don’t have any chain transfer agents

([S]=0)

1 𝑅𝑖 𝐼
= + 𝐶𝑀 + 𝐶𝐼
ത
𝑋𝑛 2𝑅 𝑝 𝑀

Odian p. 239
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 Hints, exercise 3.4

• In this case, we don’t have any chain transfer agents

(S=0)
1 𝑅𝑖 𝐼
= + 𝐶𝑀 + 𝐶𝐼
ത
𝑋𝑛 2𝑅𝑝 𝑀

• Use the steady-state assumption and known equations

for Ri and Rp to find equations for Ri and [I] that is
dependent on Rp

• In Odian, p. 238-241 might be useful

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 Hints, exercise 3.4
1
• Plot 𝑋ത as a function of 𝑅𝑝
𝑛
• To determine the values in the a)-case, use only the
linear part of the function you plotted

Note:
• If no chain transfer to initiator CI = 0.
• 1/Xn vs. Rp is straight line as equation is first order
• If chain transfer to initiator (CI  0):
• 1/Xn vs. Rp is a curve as equation is second order

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 Hints, exercise 3.4

• Remember that the experimental data obeys the

following equation (could be useful for determining 𝑓𝑘𝑑 )
𝑚𝑜𝑙
𝑅𝑝 = 4.0 ∙ 10−4 ∙ [𝐼]
𝑑𝑚3 ∙𝑠 2

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 Hints, exercise 3.4 c)

• Rearrange the equation you derived in the a)-case

1
• Plot − 𝐶𝑀 ൗ𝑅𝑝 as a function of 𝑅𝑝
𝑋ത𝑛

• In Odian, p. 238-241 might again be useful

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 During the exercise session, please
remember to:
• Keep a safe distance to other people
– 1−2 meters
– Use only every second row (2,4,6,8,10,…)

• NOT come to the exercise session on campus if you feel

sick
– Attend the virtual exercise session instead (Thursdays 12:00-
14:00 in Microsoft Teams)

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