10.

569 Synthesis of Polymers

Prof. Paula Hammond
Lecture 29: Functionalization Case Studies:
Biomaterials Systems, LC Polymers

Aromatic Substitutions
e.g. chloromethylation

SnCl4
CH2 CH CH2 CH
n n
ClCH2OCH
I

CH2Cl

good for nucleophilic

substitution

I + CH3OH + CH2 CH
N 2 NaOH n

OH
N

Other Useful Functionalizations

- can use reactive amines
e.g.

CH2 CH ⇒ NH3 + R CH2 Cl NH CH2 R

n
O
H2N
⇒ NH2 + R CH CH2 NH CH2 CH R
reactive
site epoxide
OH

- methacrylate chemistry

CH3 CH3 CH3

hydrolyze
H2C C CH2 C CH2 C
n
CO2R' CO2R' C O

OH

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

CH2 C
n
C O Used in Merrifield synthesis
OH RNH3 + DCC (step growth)
SOCl2 + EDC → activates carboxylic acid,
which is attacked by amine

CH3 CH3

CH2 C CH2 C
n n
C O C O
Cl NH

- hydrosilation
general reaction

R Si H + R Si CH2 CH2 R
R Pt
vinyl
group

on polymers

CH3 CH3
Si O + Si O
n n
H R

R
Handout
-
N

O
2-ethyl-2-oxazoline
cationic ring-opening polymerization

N N N
N
O O O
Backbone can be converted to
polyethylene amine.

10.569, Synthesis of Polymers, Fall 2006 Lecture 29

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.
Liquid Crystals (LC’s)

→ Board-shaped
“calamitic” can orient preferentially

→ disc-shaped
“discotic”

crystals orientation
domains of different orientation
guide light along domains

polydomains

Align LC → using EM field

can allow light to pass through

Applications: displays – need mechanical stability

storage – freeze in orientation and read later
glassy polymer

→ How to attach LC to polymers

1. How to form polymer w/LC side group

2. Block copolymer: LC side chain block and glassy block

10.569, Synthesis of Polymers, Fall 2006 Lecture 29

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.
Design “Case Study” – LC Side Chain Polymers

polymer
backbone
Requirements
-Backbone: determines Tg
spacer • mechanical properties
• chemical stability
• can affect switching times/
response times
LC
(mesogen)

-Alkyl spacer group

- choose spacer group: alkyl and ethylene oxide (most common)

shorter more flexible

⇓ b/c CH2O bond
leads to
nematic phases

layers

Unidirectional Stacked: 2D order

Ordered ⇒ smectic
⇒ nematic more ordered system

Longer spacers form smectic phases

alkyl group will order

-Mesogen
-LC properties
optoelectronic response
alignment
time
dipole

10.569, Synthesis of Polymers, Fall 2006 Lecture 29

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.
-Other factors
• does PDI matter?
For this application, it depends which phase you’re going for
For LC polymers, can lose some less stable phases w/high PDI

Example:

backbone
CH2 CH

C O

O O O

(CH2)5 C O O C OC4H4

PDI Increasing T →
a 1.2 SF → RN → SA → N → I
b 2.9 SF → N → I

close for
both PDI

SF = smectic F
I = isotropic clearing point
N = nematic

• High MW/Low MW?

Oligometric → stable image
High MW → storage
• Selected polymer chem. (side group react w/backbone?)
need 100% substitution?

10.569, Synthesis of Polymers, Fall 2006 Lecture 29

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.