10.

569 Synthesis of Polymers

Prof. Paula Hammond
Lecture 3: Step Growth Polymerization, Types of Monomers, Kinetics and
Equilibrium Considerations, Closed vs. Open Systems

Kinetics of Step Growth Polymerization (Chapter 2)

A + B → polymer + byproduct

Rp = rate of polymerization
−d ⎡⎣M ⎤⎦ −d ⎡⎣a⎤⎦ −d ⎡⎣b⎤⎦
Rp = = = = k ⎡⎣a⎤⎡
⎦⎣b⎤⎦
dt dt dt
a
Assume r =1, where r is the stoichiometric ratio. r =
b
⎡⎣a⎤⎦ = ⎡⎣b⎤⎦
⎣⎡a⎦⎤o
Terminology pn varies with t → pn =
⎣⎡a⎦⎤
( Xn ) p. 50
−d ⎡⎣a⎤⎦ 2
= k ⎡⎣a⎤⎦
dt

−d ⎡⎣a⎤⎦
2
= kt
⎡⎣a⎤⎦
1 1
− = kt
⎡⎣a⎤⎦ ⎡⎣a⎤⎦o

⎡⎣a⎤⎦o ⎡a⎤
− 1 = ⎡⎣a⎤⎦o kt π =1− ⎣ ⎦
⎡⎣a⎤⎦ ⎡⎣a⎤⎦o
in book, π = p (p. 46)
⎡⎣a⎤⎦o 1
=
⎡⎣a⎤⎦ 1 − π

1
⎡⎣ao ⎤⎦ kt = − 1 = pn − 1
1− π
Notes:
1
1. ⎡⎣M ⎤⎦ ∝ as time ↑, concentration of monomer ↓
t
2. pn increases linearly with time

kf kf >> kr
a+b c+d LeChatlier’s Principle: remove water
kr To drive reaction forward

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date
Making esters:
O
Keq
COOH + OH C O + H2O

Ester can hydrolyze with water and

go backwards (reverse rxn) → drug delivery

⎡COO⎤⎦ ⎡⎣H2O⎤⎦
Keq = ⎣
⎣⎡COOH ⎦⎣
⎤⎡OH ⎦⎤
Assume at t = 0 : ⎡⎣M ⎤⎦ = ⎡⎣M ⎤⎦o
Put in terms of π:
⎣⎡COO⎦⎤ = π ⎡⎣COOH ⎦⎤o = π ⎡⎣OH ⎦⎤o = π ⎡⎣M ⎦⎤o
[OH ] = “ “
⎣⎡COOH ⎦⎤ = ⎡⎣OH ⎦⎤ = ⎣⎡M ⎤⎦o − π ⎡⎣M ⎦⎤o = ⎡⎣M ⎦⎤o (1 − π )

( π ⎡⎣M ⎤⎦ )
2

o
K =
⎡⎣M ⎤⎦o (1 − π )
2 2

π2
K =
(1 − π )
2

1
K2
π= 1
In closed system, limited by K (reaction constant).
1+ K 2

That also means rxn and polymer limited by K.

1
1
pn = = 1 + K2
1− π
where pn is the # average degree of polymerization (# of units in polymer)

Polyesterification: K: 1 ∼ 10
pn ∼ 2 - 5 monomers

Polyamidation: K: 100 – 1000

pn : 10 - 40

In between: removing some of the water

Open Driven System

Removing byproduct
- H2O by temperature, low pressure, or N2 blowing of water
- Acid like HCl, base neutralization
⎡⎣H2O ⎤⎦ ↔ MW pn ( )
How H2O affects pn

10.569, Synthesis of Polymers, Fall 2006 Lecture 3

Prof. Paula Hammond Page 2 of 5

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date
 O O

COH + OH C O + H2O

⎡COO ⎦⎤ ⎣⎡H2O ⎦⎤ = π ⎣⎡H2O⎦⎤

K =⎣
⎡⎣M ⎤⎦o (1 − π )
2
⎡⎣COOH ⎤⎡
⎦⎣OH ⎤⎦

1 π ⎣⎡H2O⎦⎤eq
K = ⋅ ⋅
1 − π 1 − π ⎡⎣M ⎤⎦o

1
pn =
1− π

π 1 1− π 1
= − = − 1 = pn − 1
1− π 1− π 1− π 1− π

⎡H2O⎤eq
(
K = pn ⋅ pn − 1 ) ⎣ ⎡⎣M ⎤⎦⎦
o

⎣⎡M ⎦⎤o K
⎣⎡H2O⎦⎤eq = only get down to a certain water concentration
(
pn pn − 1 )
→ solve for best p n possible

Polyesterification Using Acid Catalysis

O OH
k1
COH + HA C OH
k2 +
-
Acid A
More active than COOH
catalyst

⎡ OH ⎤
⎢ C OH ⎥
⎢ + - ⎥
= 1 =⎣ ⎦
k A
K12
k2 [HA][COOH ]

OH OH
k3
Slow step
C OH + OH C OH
+ k4 - (rate-determining step)
- A +
A OH

10.569, Synthesis of Polymers, Fall 2006 Lecture 3

Prof. Paula Hammond Page 3 of 5

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date
 ..
OH O

..
.. k5
C OH
.. C O + H2O + HA
- k6
A +
OH catalyst regeneration

− d [COOH ]
Rp = Rate of disappearance of carboxylic monomer
dt

Rp = k3 ⎡⎣C + ( OH )2 ⎤⎦ ⎡⎣OH ⎤⎦ (from previous page)

= k3K12 ⎡⎣HA⎤⎡⎦⎣COOH ⎤⎡ ⎦⎣OH ⎤⎦

From equilibrium expression [HA] is constant because it’s regenerated.

−d ⎣⎡COOH ⎦⎤
Rp = = k ' ⎣⎡COOH ⎦⎣
⎤⎡OH⎤⎦ where k ' = k3 K12 ⎣⎡HA⎦⎤ constant
dt

Self-catalyzed: [HA] = [COOH]

−d ⎡⎣COOH ⎤⎦ 2
Rp = = k " ⎡⎣COOH ⎤⎦ ⎡⎣OH⎤⎦ where k " = k3 K12
dt

−d ⎡⎣M ⎤⎦ 3
Rp = = k " ⎣⎡M ⎦⎤ separate and integrate
dt

1 1
2k "t = 2
− 2
⎡⎣M ⎤⎦ ⎡⎣M ⎤⎦o

⎡⎣M ⎤⎦ = ⎡⎣M ⎤⎦o (1 − π )

1
(p )
2 2
= = 2 ⎡⎣M ⎤⎦o k 't + 1
(1 − π )
n 2

Much slower because of time-dependence ( t )

That’s why people add acid to drive reaction.

High Temperature
- increase k
- remove byproduct (evaporate H2O)

Bulk or mass conditions (no solvent)

- [M]o is maximum
- no need to separate product
10.569, Synthesis of Polymers, Fall 2006 Lecture 3
Prof. Paula Hammond Page 4 of 5

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date
 - viscosity η low until high π
- direct processing

Use solvent
- monomers are not miscible with each other but miscible with solvent
- allow high T
- dilute viscous media (carrier for viscous media)
→ improves processing
- improves heat and mass transfer

10.569, Synthesis of Polymers, Fall 2006 Lecture 3

Prof. Paula Hammond Page 5 of 5

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date