Biologically Relevant Polymer Presentation: Lecture 5: Interfacial Polymerizations, Application Example: Polyamides

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
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

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


Biologically Relevant Polymer Presentation: Lecture 5: Interfacial Polymerizations, Application Example: Polyamides

Uploaded by

Copyright:

Available Formats

Biologically Relevant Polymer Presentation: Lecture 5: Interfacial Polymerizations, Application Example: Polyamides

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Biologically Relevant Polymer Presentation: Lecture 5: Interfacial Polymerizations, Application Example: Polyamides

Uploaded by

Copyright:

Available Formats

10.

569 Synthesis of Polymers

Biologically Relevant Polymer Presentation

Definitions of Biologically Relevant Polymers:

• Hydrolytically degradable – Polymer undergoes hydrolytic degradation

• Bioresobable or absorbable or resorbable – Polymer breaks down into

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

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

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

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

Stereochemistry affects crystallinity.

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

Aliphatic polyesters typically undergo enzymatic breakdown via esterases such as

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

Manipulate with primary monomer structure, copolymerization.

Can create libraries of molecules:

- Most common nylons:

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

pKa ∼ 9.0 pKa ∼ 5.0 “Nylon Salt”

10.569, Synthesis of Polymers, Fall 2006 Lecture 5

- 50% wt concentration in H2O

2) Salt solution concentration to a slurry

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

⇒ High MW with time/conversion

** One way to make a polyamide

10.569, Synthesis of Polymers, Fall 2006 Lecture 5

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

For highly reactive species:

Ex: diacid chloride + diamine

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

C Cl + H2N CNH + HCl

10.569, Synthesis of Polymers, Fall 2006 Lecture 5

You might also like