10.

569 Synthesis of Polymers

Prof. Paula Hammond
Lecture 4: Common Processing Approaches, Near-equilibrium vs. Far from
Equilibrium, Homogeneous Solution and Bulk Polymerizations

Acid catalyst [HA]

1
⎡⎣a⎤⎦o kt = − 1 = pn − 1
1− π

pn linear ↑ with time

correlates
For self-catalyzed case: with

1 2 2
= pn = 2 ⎡⎣M ⎦⎤o kt + 1
(1 − π )
2

⇒ pn ↑ with t

Basic rate expression for acid catalyst:

Rp = k3 K12 ⎣⎡HA⎦⎣
⎤⎡COOH ⎦⎣
⎤⎡OH ⎦⎤
decrease

Self-catalyzed:
2
Rp = k3 K12,COOH ⎡⎣COOH ⎤⎦ ⎡⎣OH ⎤⎦ Slower reaction
Gets extremely slow at the end of the reaction

O
Polyester (k ∼ 1)
OH + COOH C O

O H
Polyamide (k ∼ 10)
C N In some cases k ∼ 100 (hungry polymer)
NH2 + COOH

Typical process conditions for near equilibrium step growth:

• High T
- to increase k (k↑ with T↑)
- to aid in byproduct removal
• Bulk or mass polymerization (no solvent)
- if the reactants are miscible (forming 1 uniform, mixed phase), get
highest concentrations possible
- no need for separations step (remove solvent)
- viscosity η low enough to process until high MW
- product can be directly processed into final form
• Solvents
- may be needed to solubilize two monomers (reactants)

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date.
 - could allow higher T to be approached without scorching polymer
- carrier (dilutant) for viscous media (exp for high MW)

Interchange Reactions in Near-Equilibrium Polymerization

(k ∼ 1-10)

Ex: polyamide (but same thing happens in polyester)

O O O O O
H H H H
H N RC NHRCOH + H N RC .. R
N C N RC OH
m x y

O
Shuffling H H
of chain
segments
O O O O O
H H H
H N RC N R C N R C NHRC OH + H NHRC OH
m y x

m+y+1

Illustration of shuffling of chain segments (redrawn

below):
O O O O O
H H H H
H N RC NHRC OH2 + H N RC N RC OH
m x .. R C N
y

O O O O H O H
H H
H N RC NHRC OH H N RC NHRC O H H
m O m
H O
H N C R N H H
x N C R N H
x
H
O R C N RC OH H
R C N RC OH
y
H H O O y
O O

Continued on next page

10.569, Synthesis of Polymers, Fall 2006 Lecture 4

Prof. Paula Hammond Page 2 of 6

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

O O
H O O H
H N RC NHRC O
m H H
C R N xH H N RC NHRC O H
m
N H O H O
H
N C R N xH
H
R C N RC OH
y H
R C N RC OH
O O y
O O

O
H
O O C R N xH
H O H O O H
H N RC NHRC N H O
m H H
H H N RC NHRC N C R N xH
R C N RC OH m
y O H
O O
H
R C N RC OH
y
O O

O O O O O
H H H
H N RC N R C N R C NHRC OH + H NHRC OH
m y x

• If no removal of byproduct (H2O)

⇒ No net change in MW
• Only if H2O is removed during interchange will MW change (increase)
⇒ Can be used to increase MW in the final form of a product

10.569, Synthesis of Polymers, Fall 2006 Lecture 4

Prof. Paula Hammond Page 3 of 6

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date.
Real Industrial Processes
Diacid + Diol → low MW polymers
Less need for high π
Crosslinked networks

Making polyethylene terephthalate (PET) (polyester)

Trade names: Mylar®, Dacron®, Terylene®

O O

C C OCH2CH2 O
n

Tm = 270oC
High mechanical strength (from aromatic group rigidity) Ideal material for
carpet, clothing,
Tough (flexibility in backbone)
photographic
Partially crystalline (adds to toughness) substrates, Boil-in-
Bag meals, PET Coke
⇒ $9.5 billion/year bottles

O O Need high MW
H2 H2 Very slow
HOC COH + HO C C OH Very expensive
Instead…

2-Step Process
1. dimethyl terephthalate

O O
.. H2 H2
H3COC COCH3 + 2 HO
.. C C OH

easy to purify, cheap ethylene glycol (EG)

O O

HO CH2CH2 OC CO CH2CH2 OH + 2 H3C OH

Methanol
(collect as it is dripped off)
10.569, Synthesis of Polymers, Fall 2006 Lecture 4
Prof. Paula Hammond Page 4 of 6

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date.
 T ∼ 150 – 210 oC
P ∼ 1 atm
Done in “solvent” of excess ethylene glycol (increase rate of forward rxn)
Detailed mechanism for above reaction:

O O O O
..
H3COC COCH3 + HO
.. CH2CH2 OH H3COC COCH3

..
HO CH2CH2 OH H O CH2CH2OH
..

..
O O O O H O CH2CH2 OH
H3COC C OCH3 H3COC C OCH3 H
O H O
CH2CH2OH CH2CH2OH

O O
O O
H3COC C O CH2CH2OH repeat
HOH2CH2CO C C OCH2CH2OH
+ HO CH3

2. T = 270oC – 280oC (increase T)

Drip stops
P = 0.5 – 1 torr (create vacuum)
Drive off EG

O O O O

n HO CH2CH2 OC CO CH2CH2 OH H OCH2CH2OC C OCH2CH2OH

n
Ester
Interlinkage + n-1 HO CH2CH2 OH

Byproduct removed
Advantages: by distillation column
1. Stoichiometry balance not needed (only one monomer)
2. Dimethyl ester more easily purified
3. Ester interchange k (rate constant) is larger than k for acid + alcohol (better
kinetics)
4. removal of ethylene glycol (EG) is cleaner than H2O removal

10.569, Synthesis of Polymers, Fall 2006 Lecture 4

Prof. Paula Hammond Page 5 of 6

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date.
 Practical Example #2: Polyester anhydrides for
Biodegradable polymer systems

1. diacid + diol → oligomeric polyester

1
O O O O O O
+ R' R'
HO R OH HO HO HO R O O R n
OH
(excess) “macromer”

2. form ester macromer dianhydride

2
O O
O O O O O O O
H3C O CH3
1 R' +
acetic anhydride R O O R O OH H3C OH
H3C O n
acetic acid
byproduct
3. melt condensation

O O O O
2
add heat O O R'
R O O R
n O m
O

polyester

- ester groups: relatively hydrolysable

- anhydride groups: can be even more hydrolytically susceptible
⇒ degradable polymer
⇒ alkyl esters, acids

10.569, Synthesis of Polymers, Fall 2006 Lecture 4

Prof. Paula Hammond Page 6 of 6

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