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PolymerizationKinetics Notes

1) Radical polymerization involves three steps: initiation, propagation, and termination. Initiation is the slow rate determining step. Propagation rapidly forms growing polymer chains through addition of monomer units. Termination occurs when two growing radicals combine or disproportionate. 2) The rate of polymer production (Rp) depends on the concentration of monomer ([M]) and active radicals ([M∙]), which in turn depend on initiator concentration ([I]) and time (t). 3) For step-growth polymerization between difunctional end groups A and B, the extent of reaction depends on the initial concentrations and reaction rate constant. Stoichiometric imbalance affects conversion but not overall reaction extent. Average molecular weight

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11 views

PolymerizationKinetics Notes

1) Radical polymerization involves three steps: initiation, propagation, and termination. Initiation is the slow rate determining step. Propagation rapidly forms growing polymer chains through addition of monomer units. Termination occurs when two growing radicals combine or disproportionate. 2) The rate of polymer production (Rp) depends on the concentration of monomer ([M]) and active radicals ([M∙]), which in turn depend on initiator concentration ([I]) and time (t). 3) For step-growth polymerization between difunctional end groups A and B, the extent of reaction depends on the initial concentrations and reaction rate constant. Stoichiometric imbalance affects conversion but not overall reaction extent. Average molecular weight

Uploaded by

retard
Copyright
© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
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Initiation step: “slow” rate determining step

𝑘𝑑
𝐼 → 2𝑅 ∙ 𝑘𝑑 ~ 10−4 − 10−6 /𝑠𝑒𝑐

Propagation step:

𝑅∙ + 𝑀 → 𝑅𝑀∙
𝐿
𝑅𝑀∙ + 𝑀 → 𝑅𝑀𝑀∙ 𝑘𝑝 ~ 102 − 104
𝑔𝑚𝑜𝑙 ∙𝑠𝑒𝑐
𝑘𝑝
∙
𝑅𝑀𝑛∙ + 𝑀 → 𝑅𝑀𝑛+1

Termination step
𝑘𝑡𝑐
Combination: 𝑅𝑀𝑥∙ + 𝑅𝑀𝑦∙ → 𝑅𝑀𝑥+𝑦 𝑅
𝑘𝑡𝑑
Disproportionation: 𝑅𝑀𝑥∙ + 𝑅𝑀𝑦∙ → 𝑅𝑀𝑥 + 𝑅𝑀𝑦

ktc + ktd = kt
𝐿
where 𝑘𝑡 ~ 106 − 108
𝑔𝑚𝑜𝑙 ∙𝑠𝑒𝑐

𝑑[𝐼]
Initiation: = −𝑘𝑑 [𝐼] 1st order kinetics
𝑑𝑡

Where [I] = concentration of the initiator at any given time, gmol/L


Where [I]0 = initial concentration of the initiator, gmol/L

⇒ [𝐼] = [𝐼]𝑜 𝑒 −𝑘𝑑 𝑡 (1)


𝑑[𝑅 ∙ ]
= 2𝑘𝑑 [𝐼] 𝑓 − 𝑘𝑝 [𝑅 ∙ ][𝑀] (2)
𝑑𝑡

f = efficiency factor (< 1)


Pseudo steady state Hypothesis ⇒ active intermediates reach
steady state rapidly, so rate of change of their concentration is
approximately zero.
𝑑[𝑅 ∙ ]
⇒ ≈0
𝑑𝑡
𝑑 [𝑅 ∙ ]
= 2𝑘𝑑 [𝐼] 𝑓 − 𝑘𝑝 [𝑅 ∙ ][𝑀] ≈ 0
𝑑𝑡

𝑑 [−𝑀∙ ]
= 𝑘𝑝 [𝑅 ∙ ][𝑀] − 2𝑘𝑡𝑐 [𝑀∙ ][𝑀∙ ] − 2𝑘𝑡𝑑 [𝑀∙ ][𝑀∙ ] ≈ 0
𝑑𝑡

= 𝑘𝑝 [𝑅 ∙ ][𝑀] − 2𝑘𝑡 [𝑀∙ ]2 ≈ 0 where 𝑘𝑡 = 𝑘𝑡𝑐 + 𝑘𝑡𝑑 (3)

𝑓𝑘𝑑 [𝐼]
(2) and (3) ⇒ 𝑓 2𝑘𝑑 [𝐼] = 2𝑘𝑡 [𝑀∙ ]2 ⇒ [𝑀∙ ] = √
𝑘𝑡

Polymer Production Rate

Molar rate of monomer consumption (gmol monomer/Liter.sec)

−𝑑[𝑀] 𝑓𝑘𝑑
𝑅𝑝 = = 𝑘𝑝 [𝑀][𝑀∙ ] = 𝑘𝑝 √ [𝑀][𝐼]0.5
𝑑𝑡 𝑘𝑡

𝑘𝑑 𝑡
𝑑[𝑀] 𝑓𝑘𝑑 −
− = 𝑘𝑝 √ [𝐼]0.5
0 𝑒 2 dt
[𝑀] 𝑘𝑡
𝑘 𝑡
[𝑀] 𝑓[𝐼] − 2𝑑
𝑙𝑛 [𝑀] = −2𝑘𝑝 ( 0 )0.5(1- 𝑒 )
0 𝑘𝑡 𝑘𝑑

Total mass of monomer consumed = Reaction volume x ([M]0 –[M]) x

mol wt of monomer

Rate of formation of polymer by mass (grams/s) =

Rate of consumption of monomer by mass (grams/sec)

Polymer “Quality”
Kinetic Chain length = average number of monomer units on a growing
polymer chain

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛


𝛾=
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑝𝑟𝑖𝑚𝑎𝑟𝑦 𝑟𝑎𝑑𝑖𝑐𝑎𝑙𝑠 𝑠𝑡𝑎𝑟𝑡𝑖𝑛𝑔 𝑎 𝑐ℎ𝑎𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝑓𝑘
𝑘𝑝 √ 𝑘 𝑑 [𝐼]0.5 [𝑀] 𝑘𝑝 [𝑀]
𝑡
𝛾= =
2𝑓𝑘𝑑 [𝐼] 2√𝑓𝑘𝑑 𝑘𝑡 [𝐼]

Degree of Polymerization 𝐷𝑃)𝑛 = 2𝛾 if termination is by combination


𝐷𝑃)𝑛 = 𝛾 if termination is by disproportionation

𝟏
Summary: 𝜸 ∝ [𝑴], [𝑰]𝟎.𝟓
BUT 𝑹𝒑 ∝ [𝑴], [𝑰]𝟎.𝟓
Step-Growth Reactions
A – A + B – B → AABB
Reaction of end-group A with end-group B can be represented as
k=rate constant
~~~A + B~~~ → ~~~AB~~~

[𝐴]0 − [𝐴] = moles of A consumed = moles of B consumed =


[𝐵 ]0 − [𝐵 ]
⇒ [𝐵 ] = [𝐵 ]0 − [𝐴 ]0 + [𝐴 ] = [𝐴 ]
if [𝐴]0 = [𝐵]0 stoichiometric balance

Molar rate of consumption of A & B end groups

𝑑[𝐴] 𝑑[𝐵]
− = 𝑘 [𝐴][𝐵] ≡ −
𝑑𝑡 𝑑𝑡

(Multiply by molecular weight to get mass rate)

𝑑[𝐴]
− = 𝑘 [𝐴][𝐴] = 𝑘 [𝐴]2
𝑑𝑡

1 1
⇒ [𝐴] − [𝐴 =𝑘 𝑡
0]
[𝐴]0 −[𝐴]
Define extent of conversion of “A” end-groups 𝑃𝐴 = [𝐴]0

[𝐴] = [𝐴]0 (1 − 𝑃𝐴 ) = [𝐴]0 − 𝑃𝐴 [𝐴]0

1
(1−𝑃𝐴 )
− 1 = 𝑘 [𝐴 ]0 𝑡
In reality, stoichiometric imbalance is always present due to impurities:
[𝐴]0
[𝐵]0
=𝑅

If A is the limiting reactant, R < 1


[𝐴 ]0 − [𝐴 ] = [𝐵 ]0 − [𝐵 ] is still correct
[𝐴]0 1
[𝐵 ] = [𝐵 ]0 − [𝐴 ]0 + [𝐴 ] = − [𝐴]0 + [𝐴]0 − 𝑃𝐴 [𝐴]0 = 𝐴0 [ − 𝑃𝐴 ]
𝑅 𝑅

Molecular weight
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 𝑚𝑎𝑠𝑠
Average molecular weight = ≡ 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒𝑛𝑑−𝑔𝑟𝑜𝑢𝑝
𝑚𝑜𝑙𝑒𝑠
2

Average degree of polymerization of reaction mixture 𝑋̅𝑛 =


𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟
𝑚𝑜𝑙𝑒𝑠 𝑒𝑛𝑑−𝑔𝑟𝑜𝑢𝑝
𝑓𝑖𝑛𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑟 2

[𝐴]0 [𝐵]0
+ 2 [𝐴]0 +[𝐵]0
= 2
[𝐴]+[𝐵] = 1
[𝐴]0 −𝑃𝐴 [𝐴]0 +[𝐴]0 ( −𝑃𝐴 )
2 𝑅

1
[𝐴]0 (1+ ) 𝑅+1
𝑅
= 1 =
[𝐴]0 [1−𝑃𝐴 +( −𝑃𝐴 )] 𝑅+1−2𝑅𝑃𝐴
𝑅

2 1
= = for R = 1
2−2𝑃𝐴 1−𝑃𝐴

𝑋̅𝑛
Degree of polymerization of polymer D𝑃𝑛 = for AA and BB type
2
monomers

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