ECHE35101: 04-26-2023

Chap 11. Kinetics of Condensation

 Chap 11

[1] Introduction
M+M M-M + H2O
M + M-M M-M-M + H2O
M + M-M-M M-M-M-M + H2O
M-M + M-M M-M-M-M + H2O
: :
M+M M-M + H 2O

e.g.) Polyesterification

O O
C OH + HO K C O + H2O

- Question: reactivity vs. molecular size?

- Assumption: independent of the size of molecules.
- Answer: yes or no.
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[2] The reactivity of large molecules

(1) Physical rationalization of assumption
① Rate of movement of the COOH and OH groups
through solution >> Rate of movement of the center of mass
② Solvent cage effect (collision)
- Molecular size Diffusion rate Collision number

K8 K9
A+B (A + B) P
K-8

d [ P] K8 K 9
= [ A][B]
dt K −8 + K9

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(2) Two-cases to consider

① K-8>>K9 : diffusion >> chemical reaction

d [ P] K 8
- Case(a) : = K9 [ A][B]
dt K −8

- Independent on the molecular size (except n≤2)

② K-8<<K9 : diffusion << chemical reaction

d [ P]
- Case(b) : = K8 [ A][B]
dt

- dependent on the molecular size

[3] Rates of Polycondensation Rxns

d [ P] d [COOH ]
- Reaction rate : =−
dt dt
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[4] Kinetics of Polycondensation

H3O
C OH + HO C OH + HO + H2O
O O
H

O H O H O
-H3O+
C OH C OH2 C O

H O O

(1) Derive esterification equation

d [COOH ]
− = k[COOH ][OH ][acid ]
dt

① Case 1 : No acidic catalyst (self catalyzed)

② Case 2 : Acid-catalyzed polyesterification

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① Case 1 : No acidic catalyst (self catalyzed)

d [COOH ]
− = k3[COOH ]2 [OH ] (k3 : Three-order rate const.)
dt

at t=0, [COOH]0 = [OH]0

d [COOH ]
− = k3[COOH ]3
dt
1 1
= + 2k3t
[COOH ]2 [COOH ]02

Conversion
[COOH ]
P = 1− , [COOH] = [COOH]0(1-P)
[COOH ]0

1
= 1 + 2[COOH ]02 k3t (Y=aX+b)
(1 − P ) 2

- obeys very well after 80% conversion

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② Case 2 : Acid-catalyzed polyesterification

d [COOH ]
− = k3 [COOH ][OH ][acid ] + kcat [COOH ][OH ][H + ]
dt
= k3 [COOH ]3 + kcat [COOH ]2 [ H + ]
= [COOH ]2 (k3 [COOH ] + k cat[ H + ])

By definition of catalyst

[H+] ~ constant

Thus, kcat[H+] >> k3[COOH]

d [COOH ]
− = k 2 [COOH ]2 (where k2 = kcat[H+])
dt
1
= 1 + k 2 [COOH ]o t
1− P

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[5] Time Dependence of the Average Degree of Pzn

& Average Molecular Weight
(1) Esterification
O O
C OH + HO C O

[COOH]0 = [COOH] + P[COOH]0 + H2O

N : total # of molecules in the system

N / V = [COOH ] = [COOH ]0 (1 − P)
V : the volume
P : conversion (0~1)

(2) Average degree of Pzn : the ratio of [COOH]0/[COOH]

[COOH ]0 1
DP = =
[COOH ] 1 − P
O O
HO C R C O R' O H
n
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- If M0 : Average MW of structural units [repeating unit]

1
Mn = M 0 + 18 (H2O)
1− P
= DP  M 0 + 18 (H2O)

eg) HOOC CH2 4

COOH + HO CH2 OH
10
112 (C6H8O2) 172 (C10H20O2)

M 0 = 284

- At high conversion (high MW)

M n (uncatalyzed )  M 0[COOH ]0 (2K3 ) 2 t

1 1
2

M n (catalyzed)  M 0[COOH ]0 K2t

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[6] Molecular –weight distributions (MWD) of linear

condensation polymers
(1) Assumption: reactivity of functional groups is independent
of the size of the molecule
eg) H2N R COOH : structural unit [repeating unit]
H O
N R C

(2) x-mer: randomly selected PMR molecule containing x

structural units (see Table 11.3)
H O O
H N R C x-1N C OH : reacted COOH : x-1/unreacted COOH : 1

Nx
Pr ob( x) = P x −1 (1 − P)1 = P : the fraction of COOH groups
N that reacted in time t
N COOH = N = N 0 (1 − P)
1-P : the fraction of COOH groups
N x = N 0 (1 − P) 2 P x −1
that unreacted in time t
Nx 2 x −1
# fraction N = (1 − P) P t : given time
0
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(3) Number Average MW from probability

- Mx-mer = xM0 (M0 : MW of repeating unit)
N0
M n =  xM 0 Pr ob( x)  Pr ob( x) = P x −1 (1 − P)
x =1
N0
= M 0  x(1 − P)P x −1
x =1
N0 
= M 0 (1 − P ) xP x −1
 xP x −1
= (1 − P) −2
x =1 x =1

NxM x M 0 xN x x(1 − P ) 2 P x −1
Wx = 
= 
= 

N M
x =1
x x M 0  xN x
x =1
 x(1 − P)
x =1
2
P x −1

Mx=M0·x from eq (40)

weight fraction of x-mer



 xP
x =1
x −1
= (1 − P) −2

- Thus, weight fraction (see Figure 11.6)

Wx = x(1 − P)2 P x−1
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(4) Weight-average molecular weight ( Mw )

Mw =  Wx M x = M 0  xWx
x x
N0
= (1 − P ) M 0  x 2 P x −1
2

x =1
N0
1 2
 xP
x =1
x −1
=(
1− P
)
N0
1+ P
 x 2 P x−1 =
x =1 (1 − P ) 3
1
Mn = M0
1− P
1+ P
Mw = M0
1− P
 M w = M n (1 + P )  M w  2M n

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[7] Effect of Nonstoichiometric Reactant Ratios

on Linear Condensation Polymers
(1) to be high MW
- stoichiometric balance
- pure enough (purity ~100%)
- no side reaction When, N B = N A / r
0 0

0  1− r 
r = NA 1 ( N A0  N B0 ) Nce = N A0 2(1 − P) +
N B0  r 
1+ r 1
N su = 1 / 2( N A0 + N B0 ) = 1 / 2 N A0 ( ) N= N ce
r 2
N A = N B 1− r
N = N A0 (1 − P + )
N B N A rN A 2r
= 0 = = rP
N B0 NB N A0 N 1+ r
DP = su =
Nce = NA + NB N 2r (1 − P) + 1 − r
N ce = (1 − P) N A0 + (1 − rP ) N B0
1
When, r =1 DP(r = 1) =
1− P
Nsu: # of structural units
1+ r
Nce: # of chain ends P =1 DP( P = 1) =
P: the fraction reacted A groups (=Conversion) 1− r
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[8] Branched and Crosslinked Condensation Polymers

ba A ba A
B
ab ab ba ab ba
4B + 9A A A ba ab ba A + 12H2O
B
ba A ba A
(1) Gelation
① Carothers’ equation
2 2 Fav : average functionality
P= −
Fav DPFav P : conversion
2
When, DP →  Pc =
Fav
2 OH O O
eg) ∴ Fav = 12/5 = 2.5
OH + 3HOC COH
Pc = 83.3%
OH
OH 6 + 2 + 8 16
2 O O Fav = = = 2.29
7 7
OH + HO OH + 4HOC COH 2
 Pc = = 87.3%(overestimated )
OH 2.29
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② Statistical Method
B B
ba ab
B B

- if f : functionality of branch point, f-1 : the residual functionality

1 αc : critical branching coeff.
c =
- Probability f −1  c ( f − 1)  1

(3) Assumption
① all functional groups are equally reactive
② all reactions take place between molecules
PB2 p rPA2 p
= =
r − PB2 (1 − p) 1 − rPA2 (1 − p)

PA, PB : the fractions of A and B that have reacted

1
 r  1+ p r : ratio of [A]/[B]
1+ p p : the fraction of original A that containing tri-or higher
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③ Case 1 : No bifunctional monomer: p = 1

1
 = rPA2 = PB2
r
④ Case 2 : [A]0=[B]0: r = 1 ; PA=PB=P
P2 p
=
1 − P 2 (1 − p)

⑤ Case 3 : [A]0=[B]0: r = 1 & no bifunctional monomer: p = 1

 = P2
eg)
2 OH O O
1
Case 3 OH + 3HOC COH r=1, p=1 P = = 0.707 70.7%
2
OH

2 OH O O 8
Case 2 r=1, p=6/8=3/4 P = = 0.756
OH + HO OH + 4HOC COH 14
OH
75.6%
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(4) Gelation from Rosen

A A A

A A A A
f =3 f =4
A A + B B + Af Af-1 A BB AA i BB A Af-1

1 2 3 4

Bond Probability
1 PA : A reacting with B
2 PB(1-p) : B reacting with A on AA
3 PA : A reacting with B on BB
4 PB p : B reacting with A on A f

p : fraction of total A groups in the A f

(1-p) : fraction of total A groups in the AA molecules
PA : probability of finding a reacted A group
PB : probability of finding a reacted B group
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(5) Overall probability

PA PB (1 − p)PA  PB p
i


 =  PA PB (1 − p) PA i PB p =
PA PB p
i =0 1 − PA PB (1 − p)

N A0 N A0 − N A N B0 − N B
r= , PA = , PB =
N B0 N A0 N B0

N A0
 PB = PA = PA
N B0

- For the stoichiometry of the rxn

N A0 − N A = N B0 − N B

N A0
 PB = PA = PA
N B0

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