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Other Polymers o

This document discusses polymerization methods for obtaining polymers through step-growth condensation reactions. It focuses on solution polymerization and alternative methods like two-phase polymerization and interfacial polymerization. Solution polymerization allows control over heat removal and viscosity but requires consideration of solvent effects. Two-phase polymerization uses an aqueous and organic phase to form polymers at the interface and provides advantages like high molecular weights without needing perfect conversions. Interfacial polymerization is further described as either quiescent or stirred processes and examples of resulting polymers are given.

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34 views5 pages

Other Polymers o

This document discusses polymerization methods for obtaining polymers through step-growth condensation reactions. It focuses on solution polymerization and alternative methods like two-phase polymerization and interfacial polymerization. Solution polymerization allows control over heat removal and viscosity but requires consideration of solvent effects. Two-phase polymerization uses an aqueous and organic phase to form polymers at the interface and provides advantages like high molecular weights without needing perfect conversions. Interfacial polymerization is further described as either quiescent or stirred processes and examples of resulting polymers are given.

Uploaded by

ÅdnAn MehmOod
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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10.

569 Synthesis of Polymers


Prof. Paula Hammond
Lecture 6: Other Polymers of Interest obtained by Step-Growth,

Polyaramids, Polyimides, Segmented and Block Copolymers from Step

Condensation Methods

Far from equilibrium polymerizations:

Processing: Bulk reactions much less desirable


- extremely reactive, exotherms huge

high concentrations further increase Rp

Better to use solution polymerization:


- can control heat removal, viscosity
- controlled by solvent choice (high capacity or low capacity solvent)

Must consider solvent effects:


- solubility of both monomers
- solubility of high MW polymer
→ wrong (poor) solvent can lead to low MW product

e.g. polyisocyanate

O O
H H2 H
O CH2CH2O C N C N C
Inherent viscosity
[dl/g, deciliter/gram]

Solvent Polarity ηinh (relative to MW)

Xylene 0.06

hazardous Chlorobenzene Cl 0.17

Nitrobenzene NO2 0.36

O
DMSO
(used in many S 0.69
biological systems) H3C CH3

For specific case of fast polymerization:


- low temps are often desired
-40oC ∼ 80oC

large ΔHexo ⇒ T ↑ can lower π ↓

- at good conditions, it is very easy to get 100% π


- lower concentrations
- slow addition of monomer(s) → control exotherm, prevent clumping

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.
Alternatives to Solution Polymerization
Two Phase Polymerization

H2O (aqueous phase) H2N-R-NH2 + Base

CH2Cl (organic phase) O O

ClC-R’-CCl
ClC-R’-CCl

ClC-R’-CCl
Draw polymer from interface
interface

Interfacial Polymerization:
1. Reactants diffuse to interface
2. Immediate reaction → perfect stoichiometry at interface

Form high MW polymer

3. Remove polymer → fresh interface


Polymerization continues until monomer is depleted in organic and/or H2O phases.

Key Differences
- Diffusion controlled (not kinetically)
- Bulk stoichiometry is irrelevant
- Treat 2 phases as reservoirs
- Higher concentrations in phases → higher mass transfer driving forces
- % conversion is not a factor in final MW

Details:
- addition of the base, HCl is generated

HCl
H2N R NH2 H3N R NH3

unprotected amine non-reactive


is very reactive

Nonreactive bases:

N Na2CO3 weak base


Pyridine
10.569, Synthesis of Polymers, Fall 2006 Lecture 6
Prof. Paula Hammond
Page 2 of 5
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.
Avoid bases with HO- (e.g. NaOH)
Because they can react with acid Cl groups:

O O O O

ClC R CCl HOC R CCl

HO

-generally true that diamine has higher diffusion rate in organic phase than diacid
chloride in H2O phase

crystall
llin
ine
e ph
phaase?

H3N-
N-RR-NH3 H2 O
film is generated at
unde
und erside of inte
terrface

organic phase
→ organic solvent ⇒ precipitant
must precipitate only high MW polymer

Advantages:
- No need for heavy refrigeration or cooling
(have very little T-increase, phases absorb exotherm)
- Get high MW without perfect conversions or stoichiometry
rate of withdrawal affects MW
when rate ∼ formation of chain formation
- Rates of withdrawal, organic solvent choice
- No high-η medium
- Polymer is readily separated from solvent and unreacted monomers

Products made this way:


- aliphatic polyamides
- aromatic polyamides
- polycarbonates
- polysulfides

10.569, Synthesis of Polymers, Fall 2006 Lecture 6


Prof. Paula Hammond
Page 3 of 5
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.
Stirred Interfacial

Organic phase (minority)


dispersed in aqueous phase

drops
∼ μm to 1 mm in size

slow stir rate → generate bubble encapsulating products


fast stir rate → continuous removal of polymer from droplet
(shear) → fine particles of polymer
shear can remove polymer film
→ fresh interface
ex. Carbon-less carbon epoxy

Polycarbonates:

R O C O
n formed from diol + carbonic acid

e.g.
O

HO C OH + C
Cl Cl
phosgene (very reactive)

O C O or
Na Na O

C
O O

Not as fast but


much safer reaction diphenyl carbonate
(much safer)

10.569, Synthesis of Polymers, Fall 2006 Lecture 6


Prof. Paula Hammond
Page 4 of 5
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.
CH3 O

O C OC
n
CH3

formed via stirred interfacial process


- high Tg ∼ 150oC
- non-crystalline (bulky CH3 groups to prevent crystalline phase the aromatic
groups would try to form)
⇒ fully amorphous → optical clarity
- tough material
- application: CDs, optical lenses, glasses, windshields

10.569, Synthesis of Polymers, Fall 2006 Lecture 6


Prof. Paula Hammond
Page 5 of 5
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.

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