10.

569 Synthesis of Polymers

Prof. Paula Hammond
Lecture 5: Interfacial Polymerizations, Application example: Polyamides

Biologically Relevant Polymer Presentation

Definitions of Biologically Relevant Polymers:

• Enzymatically degradable – Polymer degrades through enzymatic
breakdown in a biological (or ecological) environment (hydrolysis or oxidation
catalyzed by enzyme).

• Hydrolytically degradable – Polymer undergoes hydrolytic degradation

without assistance from enzyme under biologic conditions – often accelerated
by pH or pH/temperature.

• Bioresobable or absorbable or resorbable – Polymer breaks down into

remnants that are natural products readily absorbed into the body, resulting
in complete loss of original mass.

• Biocompatible – Polymer (degradable or not) does not cause a negative

reaction or induce toxicity in the presence of or in contact with tissue, blood
or organs

Erdmann, L and K. E. Uhrich. “Synthesis and Degradation Characteristics of Salicylic

Acid-derived Poly(anhydride-esters).” Biomaterials 21, no. 19 (2000): 1941-1946.

Ikada, Y. and H. Tsuji. “Biodegradable Polyesters for Medical and Ecological

Applications.” Macromolecular Rapid Communications 21, no. 3 (2000): 117-132.

Poly α-hydroxyacids are hydrolytically degradable (PLLA, PDLA, PGA, PLGA)

Poly(hydroxyalkanoates), poly(alkylene dicarboxylates) are enzymatically degradable

Polycondensation of traditional monomer yields low molecular weight oligomer

Polycondensation of cyclic monomer yields high molecular weight material

Hydrophobic, hydrophilic nature determined by R groups

For example, -CH2- groups affect hydrophobicity and make the polymer more difficult
to degrade in water

Stereochemistry affects crystallinity.

Enzymatic breakdown dependent on ability of enzyme to adsorb to the PE

macromolecule at appropriate sites.

Aliphatic polyesters typically undergo enzymatic breakdown via esterases such as

lipase (used in body to break down triacylglycerols to fatty acid and glycerol)

Aromatic polyesters are too hydrophobic and too rigid to allow binding by enzyme.

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
Lipases often ineffective on PEs with optically active center (PHB, PLLA, etc.) – PHA
depolymerase effective in some cases, others require hydrolytic degradation or other
enzymes.

Factors in degradation rate: hydrophobicity, stereochemistry, bulkiness of side

groups, and crystallinity.

Manipulate with primary monomer structure, copolymerization.

PGA, PLLA, PDLLA, and PCL have moderate glass transition temperature.

Can create libraries of molecules:

Anderson, D. G., D. M. Lynn, and R. Langer. “Semi-Automated Synthesis and
Screening of a Large Library of Degradable Cationic Polymers for Gene Delivery.”
Angew. Chem. Int. Ed. 42 (2003): 3153-3158.

Polyamides (Nylons)
Coin phrase by Dupont

- Most common nylons:

Nylon 6,6:

O O
H H2 H H2
N C N C C C
6 4 n

- aliphatic polyamides
⇒diamines + diacids
O

NH2 + HOC Keq ∼ 10 – 100 (high rate of rxn)

Commercial Syntheses
1)
O O
O H2
H2 H2 OC C CO
n H2N C NH3 + 4
HOC C COH
6 4 conc'd
H3N
H2O C
H2 6
NH3

pKa ∼ 9.0 pKa ∼ 5.0 “Nylon Salt”

basic acidic Not nylon but precursor

10.569, Synthesis of Polymers, Fall 2006 Lecture 5

Prof. Paula Hammond Page 2 of 4

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
 proton exchange salt

- 50% wt concentration in H2O

- Adjust pH of solution by titrating acid/base monomer
⇒ pH = 7.0 → stoichiometry r = 1.0
- If MW control desired, add monofunctional acid or amine

2) Salt solution concentration to a slurry

- a concentrated solution containing particles (concentrated suspension)

Raise T to ∼ 210oC, P = 250 psi (steam)

Rxn proceeds at moderate rates (water → steam → …)

3) As pn ↑, go to next stage:
T ↑ to 275oC (above Tm of Nylons)
P ↓ to 1 atm → reduces H2O

⇒ High MW with time/conversion

** One way to make a polyamide

Nylon6,6
- 50% crystallinity
- form flexible fibers: crystalline structures are strong
good H-bonding
- solvent resistance (Patagonia – clothing, carpets)

Differences in Reactivity

1.
O O O O O O

HO R OH R O Cl R Cl Cl Cl

O
diacids acid anhydride diacid chlorides phosgene
(very reactive) (extremely reactive
→ poisonous)
2. Also very reactive

10.569, Synthesis of Polymers, Fall 2006 Lecture 5

Prof. Paula Hammond Page 3 of 4

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

N C O R urethane
ROH
N C O
isocyanate RNH2 O
group
H H urethane
N C N urea

3.

HO R OH HO OH R'HN R NHR H2N R NH2

R = alkyl

For highly reactive species:

Ex: diacid chloride + diamine

+ diol Keq = 105 ∼ 108
can treat these as irreversible
→ different reaction profiles and times

- Kinetics can become diffusion controlled (stirring becomes more important)

- Highly exothermic (high ΔH)
- Need to consider heat transfer
- Short reaction times (relative to diol + diacid)

Most common:

O O

C Cl + H2N CNH + HCl

O O

C Cl + OH CO + HCl

O
OH + H
N C OH N CO no byproduct

10.569, Synthesis of Polymers, Fall 2006 Lecture 5

Prof. Paula Hammond Page 4 of 4

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