Keywords

Derive from title

Multiple word keywords
e.g. polysilsesquioxane low earth orbit
Brain storm synonyms
Without focus = too many unrelated hits
If you havent already, get it to me
today.
Research paper topics
3D Stereolithography with polymers
Plastic concrete preparation, properties & applications.
Biocompatibility of silicones
Teflon and fluoropolymers from Heaven or Hell?
Piezoelectric polymers- how they are made, why they are piezoelectric
, and applications.
Plastic in the oceans. How long do plastics last and where do they end
up?
Plastic hermetic seals
Gas separation membranes through phase inversion
Thermally induced phase separation of polymeric foams.
The strongest plastic
Major catastrophe(s) due to a polymer
Replacing ivory with plastic (comparison of composition, structure and
properties)
Plastic explosives and rocket fuels


Polymers from soybeans
Furan based polymers from corn
Bacterial and fungal attack on polymers
Conducting polymers, new metallic materials
Semiconducting polymers for PV
Semiconducting polymers for OLEDs
Polymers for stealth
Polymers for fire protection
Smart polymers that change properties with external
stimuli
Reworkable, healable or removable polymers
Photoresists
Homework
Name files with your last name, and
HWK#
Within file, your name, HWK title,
descriptive information (like the title of
you paper topic)

-Never make your audience work
Bibliography homework
Due on 27
th
at 11:59 PM
Based on your keyword search
J. Am. Chem. Soc. format with title
e.g. Doe, J., Smith, J. Proper
bibliographies for Professor Loys
class, J. Obsc. Academ. B. S. 2012, 1,
234.
Recommend endnote or pages or biblio.
Pseudoscience
An established body of knowledge which masquerades as
science in an attempt to claim a legitimacy which it would
not otherwise be able to achieve on its own terms; it is often
known as fringe- or alternative science. The most important
of its defects is usually the lack of the carefully controlled
and thoughtfully interpreted experiments which provide the
foundation of the natural sciences and which contribute to
their advancement.

Johathan Hope: Theodorus' Spiral (2003)
Examples of pseudoscience:
Intelligent design, polywater, cold fusion, N-rays,
Creationism, holistic medicine, etc
Detecting Baloney
1. The discoverer pitches the claim directly to the media.
No peer review or testing of claims is possible
2. The discoverer says that a powerful establishment is trying to
suppress his or her work.
3. The scientific effect involved is always at the very limit of
detection.
At signal noise & no one else can replicate
Requires unique instrumentation or experience
4. Evidence for a discovery is anecdotal.
5. The discoverer says a belief is credible because it has
endured for centuries.
6. The discoverer has worked in isolation.
7. The discoverer must propose new laws of nature to explain
an observation.
Polymer Phase Diagrams
Solid: amorphous glass (below glass trans) or crystalline
& Liquid (above melting point)
Polymer Tacticity: Stereochemical configuration
typical for addition or chain growth polymers
not for typical condensation or step growth polymers
Me
Me
Me
Me
H H
H H
H
H
H
H
Me Me
Me
Me
Me
H
Me
Me
H
H
H H
Me
Me Me
H
Me
Me Me
H H
H H
Me
Me
H
atactic
isotactic
syndiotactic
Me
O
OMe
n
Polymer Tacticity: Polymethylmethacrylate (PMMA)
Free radical - atactic
Anionic - isotactic
Me Me
Me Me
O
O
O
O
O
O
O
O
Me
Me
Me Me
Me Me
Me
Me
O
O
O
O
O
O
O
O
Me
Me
Me Me
Me
O
Me
O
isotactic syndiotactic
Why is this important?
Tacticity affects the physical properties
Atactic polymers will generally be amorphous,
soft, flexible materials
Isotactic and syndiotactic polymers will be
more crystalline, thus harder and less flexible
Polypropylene (PP) is a good example
Atactic PP is a low melting, gooey material
Isoatactic PP is high melting (176), crystalline,
tough material that is industrially useful
Syndiotactic PP has similar properties, but is
very clear. It is harder to synthesize
Step Growth Configurations
H
N
O
HN
1
2
3
4
5
6
O
H
N
O
N
H
O
H
N
O
n
Nylon-6
Step Growth Configurations
H
N
N
H
O
O
1
2
3
4
5
6
NH
O
O
NH
N
H
1
O
2
3
4
5
6
O
H
N
HN
O
N
H
O
N
H
H
N
O
O
n
Nylon 6,6
mp 265 C
tg 50 C
Chapter 2: Synthesis of
Polymers
1) Step Growth

2) Chain Growth
Two major classes of polymerization mechanisms
Step Growth Polymerization:
Condensation
HO
2
C CO
2
H
HO
OH
terephthalic acid
ethylene glycol
O
O O
O
n
1:1 monomer ratio
Poly(ethylene terephthalate)
or PET or PETE = polyester

Two equivalents of water is lost or condensed for each
equivalent of monomers
Dacron if a fiber
Step Growth Polymerization:
Condensation
HO
2
C CO
2
H
HO
OH
terephthalic acid
ethylene glycol
O
HO O
O
OH
O
HO O
O
OH
HO
OH
O
O O
O
OH
HO
-H
2
O
-H
2
O
Biaxially stretched PETE is Mylar
Step growth systems
Epoxies
Polyurethanes & ureas
Nylon & polyesters
Kevlar
Polyaryl ethers (PEEK)
Polysulphones
Polyimides
Polythiophenes & Photovoltaic polymers
Polysulfides and polyphenyl ether

H
2
N
R
NH
2
R'
O
Cl
O
Cl
AA
BB
Mechanics of Step Growth:
Many monomers
All are reactive
Each has
functionality of 2;
Can make two
bonds
R'
O
O
N
H
R
H
N
n
Linear, soluble
Nylon polymer
Mole fraction Conversion = 1 [COCl]/[COCl]
0
Mechanics of Step Growth:

NH
2
R
H
2
N
R'
O
Cl
O
Cl
H
2
N
R
NH
2
H
2
N
R
NH
2
NH
2
R
H
2
N
H
2
N
R
NH
2
H
2
N
R
NH
2
H
2
N
R
NH
2
H
2
N
R
NH
2
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
H
2
N
R
NH
2
H
2
N
R
NH
2
R'
O
Cl
O
Cl
NH
2
R
H
2
N
H
2
N
R
NH
2
H
2
N
R
NH
2
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
H
2
N
R
NH
2
R'
O
Cl
O
Cl
NH
2
R
H
2
N
R'
O
Cl
O
Cl
NH
2
R
H
2
N
R'
O
Cl
O
Cl
H
2
N
R
NH
2
R'
O
Cl
O
Cl
34 COCl groups; p = 1 - [COCl]/[COCl]
0
= 0 conversion
Mechanics of Step Growth: Monomer & Dimers

NH
2
R
H
2
N
R'
O
Cl
O
Cl
H
2
N
R
NH
2
H
2
N
R
NH
2
NH
2
R
HN
H
2
N
R
NH
H
2
N
R
NH
2
H
2
N
R
NH
2
H
2
N
R
NH
2
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
O
Cl
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
O
Cl
R'
O
Cl
O
Cl
H
2
N
R
NH
2
H
2
N
R
NH
2
R'
O
Cl
O
Cl
NH
2
R
HN
H
2
N
R
NH
2
H
2
N
R
NH
2
R'
O
Cl
O
Cl
R'
O
Cl
O
Cl
R'
O
O
Cl
H
2
N
R
NH
2
R'
O
Cl
O
Cl
NH
2
R
H
2
N
R'
O
Cl
O
Cl
NH
2
R
H
2
N
R'
O
Cl
O
Cl
H
2
N
R
NH
R'
O
O
Cl
30 reactive groups p = 1 - [COCl]/[COCl]
0
= 1-30/34 = 0.11
NH
R
HN
R'
O
O
H
2
N
R
NH
2
HN
R
NH
2
NH
R
HN
H
2
N
R
NH
HN
R
NH
2
H
2
N
R
NH
H
2
N
R
NH
2
R'
O
Cl
O
R'
O
Cl
O
Cl
R'
O
O
Cl
R'
O
O
R'
O
Cl
O
R'
O
O
Cl
R'
O
O
Cl
R'
O
O
Cl
H
2
N
R
NH
2
H
2
N
R
HN
R'
O
O
Cl
NH
2
R
HN
H
2
N
R
H
N
HN
R
NH
2
R'
O
Cl
O
Cl
R'
O
O
Cl
R'
O
O
Cl
HN
R
NH
2
R'
O
Cl
O
Cl
NH
2
R
H
2
N
R'
O
O
Cl
NH
2
R
HN
R'
O
Cl
O
Cl
H
2
N
R
NH
R'
O
O
Cl
Mechanics of Step Growth: Monomer & Dimers &
Trimers

19 reactive groups p = 1 - [COCl]/[COCl]
0
= 1-19/34 = 0.44
Mechanics of Step Growth: Monomer, Dimers,
Trimers, & Tetramers

13 reactive groups p = 1 - [COCl]/[COCl]
0
= 1-13/34 = 0.62
NH
R
HN
R'
O
O
H
N
R
NH
2
HN
R
NH
2
NH
R
HN
H
2
N
R
NH
HN
R
NH
2
H
2
N
R
NH
H
2
N
R
NH
2
R'
O
Cl
O
R'
O
Cl
O
Cl
R'
O
O
Cl
R'
O
O
R'
O
Cl
O
R'
O
O
Cl
R'
O
O
R'
O
O
H
2
N
R
NH
2
H
2
N
R
HN
R'
O
O
Cl
NH
2
R
HN
H
2
N
R
H
N
HN
R
NH
R'
O
Cl
O
R'
O
O
Cl
R'
O
O
HN
R
NH
R'
O
Cl
O
NH
2
R
N
H
R'
O
O
Cl
HN
R
HN
R'
O
O
Cl
HN
R
NH
R'
O
O
Cl
7 reactive groups p = 1 - [COCl]/[COCl]
0
= 1-7/34 = 0.80
NH
R
HN
R'
O
O
H
N
R
NH
2
HN
R
NH
NH
R
HN
H
2
N
R
HN
HN
R
NH
2
H
2
N
R
NH
HN
R
NH
2
R'
O
O
R'
O
O
Cl
R'
O
O
R'
O
O
R'
O
O
R'
O
O
Cl
R'
O
O
R'
O
O
NH
R
NH
H
2
N
R
HN
R'
O
O
NH
2
R
HN
HN
R
NH
HN
R
NH
R'
O
Cl
O
R'
O
O
Cl
R'
O
O
HN
R
NH
R'
O
Cl
O
NH
R
N
H
R'
O
O
NH
R
NH
R'
O
O Cl
HN
R
H
N
R'
O
O
Cl
Mechanics of Step Growth: Monomer, Dimers,
Trimers, Tetramers & Higher

3 reactive groups p = 1 - [COCl]/[COCl]
0
= 1-3/34 = 0.91
Mechanics of Step Growth: Monomer, Dimers,
Trimers, Tetramers & Higher

N
H
R
H
N
R'
O
O
HN
R
NH
HN
R
NH
H
N R
HN
H
2
N
R
HN
HN
R
NH
H
2
N
R
NH
N
H
R
NH
2
R'
O
O
R'
O
O
R'
O
O
R'
O
O
R'
O
O
R'
O
O
Cl
R'
O
O
R'
O
O
NH
R
NH
HN
R
HN
R'
O
O
HN
R
NH
H
N
R
N
H
HN
R
NH
R'
O
O
R'
O
O
R'
O
O
HN
R
NH
R'
O
O
NH
R
N
H
R'
O
O
NH
R
NH
R'
O
O Cl
H
N
R
N
H
R'
O
O
Cl
1 reactive groups p = 1 - [COCl]/[COCl]
0
= 1-1/34 = 0.97
Mechanics of Step Growth: Monomer, Dimers,
Trimers, Tetramers & Higher

NH
R
HN
R'
O
O
HN
R
NH
HN
R
NH
HN
R
N
H
HN
R
HN
HN
R
N H
H
2
N
R
NH
NH
R
NH
R'
O
O
R'
O
O
R'
O
O
R'
O
O
R'
O
O
R'
O
O
Cl
R'
O
O
R'
O
O
NH
R
NH
HN
R
HN
R'
O
O
HN
R
NH
HN
R
NH
HN
R
NH
R'
O
O
R'
O
O
R'
O
O
HN
R
NH
R'
O
O
NH
R
N
H
R'
O
O
NH
R
NH
R'
O
O
H
N
R
N
H
R'
O
O
1 reactive groups p = 1 - [COCl]/[COCl]
0
= 1-1/34 = 0.97
Mechanics of Step Growth: Monomer, Dimers,
Trimers, Tetramers & Higher

NH
R
HN
R'
O
O
HN
R
NH
HN
R
NH
HN
R
N
H
HN
R
HN
HN
R
N H
H
2
N
R
NH
NH
R
NH
R'
O
O
R'
O
O
R'
O
O
R'
O
O
R'
O
O
R'
O
O
Cl
R'
O
O
R'
O
O
NH
R
NH
HN
R
HN
R'
O
O
HN
R
NH
HN
R
NH
HN
R
NH
R'
O
O
R'
O
O
R'
O
O
HN
R
NH
R'
O
O
NH
R
N
H
R'
O
O
NH
R
NH
R'
O
O
H
N
R
N
H
R'
O
O
If R = R = Phenylene = Kevlar
Mw = 4014 g/mol
Step-Growth Polymerization
Because high polymer does not form until the end of the
reaction, high molecular weight polymer is not obtained
unless high conversion of monomer is achieved.

X
n
=
1
1 p
X
n
= Degree of polymerization
p = mole fraction monomer
conversion
1
10
100
1000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction Conversion (p)
D
e
g
r
e
e

o
f

P
o
l
y
m
e
r
i
z
a
t
i
o
n
Degree of Polymerization for step growth polymers
X = [COCl]
0
/[COCl] = 1/1-p
X or DP = 1/(1-p) = 1/1-0.97 = 1/0.03 = 33
Mechanics of Step Growth: Monomer, Dimers,
Trimers, Tetramers & Higher

NH
R
HN
R'
O
O
HN
R
NH
HN
R
NH
HN
R
N
H
HN
R
HN
HN
R
N H
H
2
N
R
NH
NH
R
NH
R'
O
O
R'
O
O
R'
O
O
R'
O
O
R'
O
O
R'
O
O
Cl
R'
O
O
R'
O
O
NH
R
NH
HN
R
HN
R'
O
O
HN
R
NH
HN
R
NH
HN
R
NH
R'
O
O
R'
O
O
R'
O
O
HN
R
NH
R'
O
O
NH
R
N
H
R'
O
O
NH
R
NH
R'
O
O
H
N
R
N
H
R'
O
O
If R = R = Phenylene = Kevlar
Mw = 4014 g/mol
Impact of percent reaction, p, on DP
if p = DP =
0.5 2
0.7 3.3
0.9 10
0.95 20
0.99 100
0.999 1000
Degree of Polymerization, D.P. = No / N = 1 / (1 - p)
Assuming perfect
stoichiometry
DPmax= (1 + r) / (1 - r) where r
molar ratio of reactants
if r = [Diacid] / [diol] = 0.99, then
DPmax= 199
Effect of Extent of
reaction on
Number
distribution
Effect of Extent of
reaction on weight
distribution
Problems in Achieving High D. P.
1. Non-equivalence of functional groups
a. Monomer impurities
1. Inert impurities (adjust stoichiometry)
2. Monofunctional units terminate chain
b. Loss of end groups by degradation
c. Loss of end groups by side reactions with media
d. Physical losses e. Non-equivalent reactivity
f. Cyclization
. Unfavorable Equilibrium Constant
Impact of Thermodynamics
Esters from Acids and alcohols K
eq
= 1-10


Amides from Acids and amines K
eq
= 10-1000


Amides or esters from acid chlorides, K
eq
>10
4

Interfacial Polymerization: Nylon Rope trick
Diamine, NaOH, in H
2
O
Adipoyl chloride
in hexane
Nylon 6,6
Driving Reactions forward
with physics
O
Cl
O
Cl
H
2
N
NH
2
hexane-1,6-diamine
hexanedioyl dichloride
or adipoyl chloride
O
O
HN
N
H n
Biaxially stretched PETE is Mylar
T
g
= 70 C
T
m
= 265 C
O
O O
O
n
O
O
O
O
n
T
g
< 0 C
T
m
= 50 C
O
HO O
O
OH
O
O O
O
HO
O
HO O
O
OH
-H
2
O
O
OH
O
O
Step Growth Polymerization:
Condensation
Each reaction occurs at approximately the same rate.
Any monomer or growing oligomer can participate

O
HO
O
O O
O
HO
O
HO O
O
OH
-H
2
O
O
O
Step Growth Polymerization:
Condensation
Impurities will kill growth and limit molecular weight
Delayed commercialization of condensation polymers
Dr. Wallace Hume Caruthers
Head of DuPont Organic research Labs
50 patents
Nylon
Polyester
Polychoroprene (Neoprene)
The Guy who got the ball rolling
More Step Growth (Condensation)
Polymers & their monomers
HO
2
C CO
2
H
terephthalic acid
diaminobenzene
O
NH O
HN
n
Kevlar
NH
2
H
2
N
T
g
= NA
T
m
= 500 C
Nomex and Technora
Twaron (AKZO)
Stephanie Louise
Kwolek (DuPont)
Polyaramides
O
H
N
H
N
O
n
Polyamides via Condensation -- Nylon 66
C
-
(CH
2
)
4
-
C
O O
O O
H
H
CH
2
-
(CH
2
)
4
-
CH
2
NH
2
NH
2
+
slight excess
C
-
(CH
2
)
4
-
C
O O
O
-
O
-
(CH
2
)
4
CH
2
CH
2
NH
3
+ NH
3
+
Nylon Salt
60% Slurry
200 C, 15 Atm. 1 hr
NH
3
+
(CH
2
)
6
-
NH
-
C
-
(CH
2
)
4
-
C
-
NH
-
(CH
2
)
6
-
NH
-
C
-
(CH
2
)
4
-
C
O
O O
O
O
-
8-10
270-300 C, 1hr
-
H
2
O
NH
-
(CH
2
)
6
-
NH
-
C
-
(CH
2
)
4
-
C
O
O
Nylon 6 6
mp. 265C, Tg 50C,
MW 12-15,000
Unoriented elongation
780%
More Step Growth (Condensation)
Polymers & their monomers
T
g
= 150 C
T
m
= 267 C
Me
Me
HO
OH
Cl Cl
O
Bisphenol A
phosgene
Me
Me
O
O
O
n
Polycarbonate
Lexan
Two phase: interfacial polymerization
More Step Growth (Condensation)
Polymers & their monomers
T
g
= 200 C; Films pressed at 250 C
Use temperature < 175 C
Stable in air to 500 C
Self-extinguishing


Me
Me
O O
S Cl
Cl
O
O
Me
Me
O O
S
O
O n
Na
Na
-2n NaCl
Polysulfone
Mw = 60-250K
More Step Growth (Non-condensation)
Polymers & their monomers
ONC CNO
n
Polyurethane
HO OH
H
N
H
N
O
O
O
O
isocyanates
Polyphenylene Oxide (PPO)
R
1
R
2
OH
+
n/2 O
2
R
1
R
2
O O
R
2
R
1
+ n H
2
O
cat
cat =
N
N
CH
3
CH
3
N
CH
3
CH
3
3 : 1
or
10:1
Cu
+
Amine Complex
Noryl is a blend with polystyrene
Oxidative Coupling Process
Mn 30,000 to 120,000
Amorphous , Tg ~ 210C
Crystalline, Tm ~ 270C
Brittle point ~ -170C
Thermally Stable to ~ 370C
Step Growth Polymers
Polyesters, polyamides, engineering
plastics such as polysulfones,
polyetherether ketones (PEEK),
polyurethanes.
Condensation often occurs.
Polymerization affords high MW late in
the game
Me
NCO
HO
OH
OCN
Me
N
H
N
H
O
O
O
O
n
Step-Growth
Non-Condensation Polymerization
Polyurethanes
1,4-toluenediisocyanate + 1,3-propanediol
[RCO
2
]
2
SnBu
2

OCN
OCN
NCO
HO
OH
OH
NH
HN
N
H
O
O
O
O
O
O
O
O
O
O
NH
HN
N
H
O
O
O
O
O
O
1 1
Functionalities > 2: Crosslinking into networks
f = 3
Polyurethanes
(thermoset)
Thermosets
Urethanes
Epoxies
Polyesters (2-stage)
Formaldehyde-aromatic
Melamine-formaldehyde

Generally: Start as low viscosity liquids (low Mw)
And set or cure to form glassy vitrified solids.
Gelation: f > 2
If f > 2
No cyclics form
then an infinite network is possible
(unless it phase separates!!!)
f = 3
f = 4
f = 4
f = 3
f = 4 f = 6
f = 6
f = 4
f = 8
f = 8 f = 8
f = 14
Functionality Higher than Two
Phase separation
= gels, glasses,
or precipitates
Due to
chemica
l
bonding
Functionality = Two: Linear polymers
f = 2
f = 2
f = 2
f = 2
f = 2
f = 2
Physical gels may form due to poor solubility of polymer
Functionality = Three: Cyclization
Lowers functionality & delays (or even prevents) gelation
f - 14
f = 8
Gel point = 1/(f -1) = 1/2 or 50% conversion
If cyclics present, gel point is higher.
Addition Polymerizations
R
R
n
1) Catalyzed polymerization
free radical
cationic
anionic
coordination
2) Active group on end of polymer
3) MW increases more rapidly
4) Cheap & easier than step growth
5) Enthalpically favorable
Free Radical Polymerizations
Initiators (catalyst):
Thermal: azo compounds, peroxides,
Redox: persulfates
Photochemical: azo, peroxides,
amine/ketone mixtures
Monomers

R
R
R
R
R
R
R
R
R
R
R
R
R
R
Usually
polymerize
Almost never
polymerize
Polymerize fine
Almost never
polymerize
Seldom polymerize
Free radical Mechanism
Initiation:
N
N
NC
NC
A
NC CN
N
2
or hv
E
a
= 140 160 kJ mol
-1
K
d
= 8 x 10
-5
s
-1
t
1/2
= 10 h at 64 C
Propagation:
R
R
NC
k
p
R
CN
R
Termination:
R
CN
R R
NC
R R
CN
R
R
NC
R
R
CN
R R
NC
R R
CN
R
R
NC
R
H
H
] M ][ M [ k R
p p
=
k
p
= 10
2
- 10
4
L/mol s
k
t
= 10
6
- 10
8
L/mol s

2
t t
] M [ k 2 R =
Free Radical Polymerization
Kinetics
MW
TIME
MOST POLYMERS FORM IN SECONDS
OR LESS
POLYMERIZATIONS TAKE HRS
R
p
[M]; R
p
[I]
1/2

Living Radical Polymerizations:

1) Atom TransfeR Polymerization (ATRP)
2) Polymerization (RAFT)
3) TEMPO


MW increases linearly with time
Narrow Mw distributions
Block copolymers
Lower concentration of propagating species
Lower termination rate
Cationic Polymerizations:

R
cat
R
cat
R
cat
R R
cat
R R
cat
R R
-H
+
R = OR, NR
2
, Ph, vinyl, alkyl
H
+
O O
H
O
HO
O
O
n
Ring opening polymerization
Vinyl polymerization
Anionic Polymerizations:

R
R
n
R = Ph, vinyl, CO
2
R, CN
R
n
n
R
R
H, Me,
cat
cat
cat = Alkyl or aryl Lithium, sodium naphalide, alkyl Grignard, some alkoxides
Vinyl polymers
Diene polymers
Anionic Polymerizations:

O
R
H
O
R
n
cat.
R = H, Alkyl
O
R
cat
R = H, Me
O
R
n
Polyacetals or carbonyls
Poly ethers
Anionic Polymerizations:

Si
O
Si O
Si
O
Si O
Me
Me
Me
Me
Me
Me
Me
Me Si
O
Si
O
Si
O
Si
O
Me
Me
Me
Me
Me
Me
Me
Me
n
Alkoxides
Polysiloxanes
Coordination Polymerizations:

Transition Metal Mediated Polymerizations
-Ziegler Natta polymerizations (Early TM)
-ring opening metathesis polymerization (metal
Alkylidenes)
-Insertion polymerizations (mid to late TMs)
Ziegler Natta Polymerizations
ZN are heterogeneous; solid catalysts
Catalytic polymerizations
Early TM halide, AlR
3
on MgCl
2

Polypropylene and HDPE
Highly productive: 10
6
g polymer/gram
catalyst-hour
10,000 turn overs/second (enzyme like
speed)-diffusion limited
Stereochemical control:
R
R
n
TiCl
4
, AlMe
3
Karl Ziegler (1898-1973)
Giulio Natta (1903-1979)
iso or syndiotactic polymers
Ziegler Natta Monomers
R
o-olefins
styrenes
R
R = alkyl, aryl
Not compatible with heteroatoms (O,N,S,etc)
Polymers Synthesized with Complex Coordination
Catalysts
Plastics
Polyethylene, high
density (HDPE)


Polypropylene,
isotactic


Polystyrene,
syndiotactic

Bottles, drums,
pipes, sheet,
film, etc.
Automobile and
appliance parts,
rope, carpeting
Specialty
plastics
Ring Opening Metathesis
Strained Rings with C=C bonds
Metal alkylidene catalysts
Ti, Mo, W alkylidenes (Schrock catalysts)
Ruthenium alkylidenes (Grubbs catalysts)
Living polymerizations
Ru
PCy
3
Ph
N N
Cl
Cl
n
Examples of ROMP
Me
No Reaction
R
R
n
R OH, NH, CO
2
H,
No strain, no polymer
n
O
O
n
Acyclic Diene Metathesis Polymerization
R
Schrock or
Grubbs
catalyst
-CH
2
=CH
2
R
n
Coordination-Condensation polymerization
Ethylene gas is produced
Not commerciallized
Redox Polymerizations
H
N
anodic
oxidative
polymerization
H
N
n
H
N
H
N
n
[O]
H
N
N
H
N
H
N
H
N
H
H
H
N
H
N
H
H
H
-2H
+
N
H
N
H
Polypyrrole
Redox Polymerizations
-2H
+
NH
2 NH
2
NH
2
N NH
2
H
H
H
N NH
2
H
N NH
2
H
n
Polyaniline
When acid doped: conducting polymer
Polymerization Techniques
Bulk-no solvent just monomer +
catalysts
Solution Polymerization-in solvent
Suspension-micron-millimeter spheres
Emulsion-ultrasmall spheres
Less Common Polymerization
Techniques
Solid state polymerization
Polymerization of crystalline monomers
Diacetylene crystals
Gas Phase polymerization
Parylene polymerizations
Plasma polymerization
Put anything in a plasma

Plasma Polymerization
Characterization of Polymers

1
H &
13
C Nuclear Magnetic Resonance
spectroscopy (NMR)
Infrared spectroscopy (Fourier
Transform IR)
Elemental or combustion analyses
Molecular weight

Polymerization Techniques
Bulk-no solvent just monomer +
catalysts
Solution Polymerization-in solvent
Suspension-micron-millimeter spheres
Emulsion-ultrasmall spheres
Bulk Polymerizations
Rare
Overheat & explode with scale up
No solvent-just monomer
Polymer usually vitrifies before done
Broad MW distribution
Acrylic sheets by Bulk polymerization of MMA
Storage of vinyl monomers in air = peroxide
initiated polymerizations
Tankcar of styrene
2005 in Ohio
Solution Polymerization
Better control of reaction temperature
Better control of polymerization
Slower
Not very green-residual solvent

Suspension Polymerization
Oil droplets dispersed in water
Initiator soluble in oil
Greener than solution polymerization
Filter off particles of polymer
Emulsion
Polymerization
Still oil in water (or the reverse)
Initiator in water
Smaller particles (latex)
Excellent control of temp
Solution turns white
Polystyrene latex
Suspension Emulsion Mini-emulsion Micro-emulsion
Monomer in oil Monomer in oil Monomer in oil Monomer in oil
Initiator in oil Initiator in water Initiator in water Initiator in water
Less Common Polymerization
Techniques
Solid state polymerization
Polymerization of crystalline monomers
Diacetylene crystals
Gas Phase polymerization
Parylene polymerizations
Plasma polymerization
Put anything in a plasma

Solid State Polymerizations
Heating Oligomeric Condensation
Polymers

T
g
< X < T
m

Nylons, Polyesters
O
O
O
O
O
HO O
O
O
n
O
O
O
O
O
O O
O
O
n
OH
250 C
HO
OH
Nylon 66 T
g
= 70 C and T
m
= 264
C
T
g
= 67 C and T
m
= 265 C
Solid State Polymerizations
Topological Polymerizations: Polymerization of crystals
Quinodimethane polymerizations
Di- and Triacetylene polymerizations
In single crystals
Solid State Polymerizations of Fullerenes
Topological polymerization in 3-D
Gas Phase Polymerization
1) Light olefins
2) Parylenes
LIGHT OLEFINS
Ethylene and propylene

2004 Global PE Demand: 136 Billion Pounds
Food Packaging
Hygiene & Medical
Consumer & Ind. Liners
Stretch Films
Agricultural Films
HDSS
Film
SOURCE: Nexant/ChemSystems 2005, PTAI 1/05
Types of Polyethylene
O
O
O
O
O
O
O
O
O
O
C-OH
O
HDPE (0.940-0.965)
High Density
LLDPE (0.860-0.926)
Linear Low Density
LDPE (0.915-0.930)
Low Density
High Pressure Copolymers
(AA, VA, MA, EA)
Gas Phase Polymerization: Light olefins


Oxygen initiator
2-3K atmospheres
250 C
Gas Phase Polymerization: Light olefins


Fluidized bed polymerization


MORE
FLEXIBLE
Gas Phase Polymerization: Paralene


Gas phase
Polymerizes on contact
Conformal coatings
Pinhole free
Preserving artifacts (paper)
Microelectronics
Medical devices
Plasma Polymerization
500 - 1 micron thick films
Continuous coatings
Solvent free
High cohesion to surface
Highly cross-linked
Generally amorphous
Plasma Polymerization
Monomers: Hydrocarbons
Double or triple bonds nice, not necessary
Fluorocarbon
Tetraalkoxysilanes (for silica)
P- pumps; PS-power supply; S-substrate
M-feed gas inlet; G-vacuum gauge
Fig1. Bell-jar type reactors
Fig 2. Tubular-type reactors
Plasma Polymerization
Plasma Polymerization
PET [Poly(Ethylene Terephthalate)]
Multi-layer bottles
No loss of fizz
Characterization of Polymers

1
H &
13
C Nuclear Magnetic Resonance
spectroscopy (NMR)
Infrared spectroscopy (Fourier
Transform IR)
Elemental or combustion analyses
Molecular weight

13
C NMR is a very powerful way to determine
the microstructure of a polymer.

13
C NMR shift is sensitive to the two
stereocenters on either side on sptectrometers
> 300 MHz. This is called pentad resolution.
r m m r m r
mmrm pentad
m = meso (same orientation)
r = racemic (opposite orientation)
1 2 1 2
13
C NMR spectrum of CH
3

region of atactic polypropylene

Infrared Spectroscopy: Bond vibrations
2-16 Micron wavelength range
polystyrene
C=C-H
C-H
C=C
stretch
Infrared Spectroscopy: Bond vibrations
Poly(methyl methacrylate)
C=O
C-O
C-H
stretch
C-H bend
Types of Addition Polymerizations
Ph
Anionic
C
3
H
7
Li
C
4
H
9
Ph
Li
+
Ph
n
C
4
H
9
Ph Ph
Li
+
n
Ph
Radical
PhCO
2

Ph
n
Ph
Cationic
Cl
3
Al OH
2
H
Ph
HOAlCl
3
Ph
n
H
Ph Ph
n
HOAlCl
3
PhCO
2
Ph
PhCO
2
Ph Ph
n
Chemical Modification of Polymers
1) Hydrolysis


2) Oxidation


3) Photochemistry
(can be oxidation or not)


4) Chemical crosslinking


5) Chemical modification
O
O
CH
3
n NaOH
H
2
O
OH
n
O
O
H
3
C
n
Na
+
Polyvinylacetate
polyvinyl alcohol
O
n
H
Poly ethylene oxide
hv, O
2
or ascorbic
acid
Me
O
H
Si
Si
Si
Si
Si
R
R
R R
R R
R
R
R
R
Polysilane
hv: UV
O
2
Si
O
Si O
Si
O
Si O
R
R
R
R
R
R
R
R
H
polybutadiene
S
8
A
S
S
S
See next slide
Chemical Modification of Polyvinyl Alcohol to make
Polyvinyl butyral for safety glass
polyvinyl alcohol
OH OH OH OH OH
CH
3
CH
2
CH
2
CHO
O O OH O O
poly vinyl butyral
No PVB
With PVB
Bullet Proof Glass
glass, laminates and polycarbonate
sheets are interlaid in a clean room to
ensure clarity. In our large autoclave,
superheated steam seals the layers
together.
Making bullet proof glass
Polycarbonate is
Strong Material
Young's modulus (E) 2-2.4 Gpa
Tensile strength (t) 55-75 Mpa
Exploding CDs
Mythbusters:
> 23,000 rpm CD will shatter
Scratches or defects are the culprit
52X drive -MAX: 27,500 rpm
typical: 11,000 rpm
10,000 RPM = 65 m/s = 145 mph
7200 gravities of acceleration
And approx. 5 MPa stress
Yield Strength 60 MPa
Nalgene
Polycarbonate Properties
Density: 1.2 g/cc
Young's modulus (E) 2-2.4 Gpa
Tensile strength (t) 55-75 Mpa
Elongation () @ break 80-150%
Glass transition (Tg) 150 C
Melting (Tm) 267 C
Upper working temperature 115-130 C
$7.3-11/kg
Bisphenol and Endocrine System
100-250 g bisphenol per Liter water in water bottles
20 g/Liter per day can disrupt mouse development
vom Saal, F.S., Richter, C.A., Ruhlen, R.R. Nagel, S.C. and Welshons, W.V. Disruption of laboratory
experiments due to leaching of bisphenol a from polycarbonate cages and bottles and uncontrolled
variability in components of animal feed. Proceedings from the International Workshop on
Development of Science-Based Guidelines for Laboratory Animal Care, National Academies Press,
Washington DC, 65-69, 2004.
Immune system
Antioxidant enzymes
Decreases plasma testosterone
Learning disabilities
vom Saal, F.S., Nagel, S.C., Timms, B.G. and Welshons, W.V. Implications for human health of the extensive
bisphenol A literature showing adverse effects at low doses: A response to attempts to mislead the public.
Toxicology, 212:244-252, 2005.
Nalgene Substitutes-food and water
Glass (blender, pitchers, glasses)
Metal (water bottles)
Polyethylene (water bottles)
Polyamide or Nylon (baby bottles)