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Polymers: Introduction
Polymer: High molecular weight molecule made
up of a small repeat unit (monomer).
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A A A A A A A A A A A A A A A A A A A A A A A A A
Monomer: Low molecular weight compound that
can be connected together to give a poymer
Oligomer: Short polymer chain
Copolymer: polymer made up of 2 or more
monomers
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monomers
Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B
Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B
Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B
Types of Polymers
Polymer Classifications
Thermoset: cross-linked polymer that cannot be
melted (tires, rubber bands) ( , )
Thermoplastic: Meltable plastic
Elastomers: Polymers that stretch and then return to
their original form: often thermoset polymers
Thermoplastic elastomers: Elastic polymers that can
be melted (soles of tennis shoes)
P l F ili
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Polymer Families
Polyolefins: made from olefin (alkene) monomers
Polyesters, Amides, Urethanes, etc.: monomers linked
by ester, amide, urethane or other functional groups
Natural Polymers: Polysaccharides, DNA, proteins
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Common Polyolefins
Monomer Polymer
Ethylene
H
3
C
CH
3
n
Repeat unit
Polyethylene
CH
3
CH
3
n
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
Propylene
Polypropylene
Ph
CH
3
n
Ph Ph Ph Ph Ph Ph Ph
Styrene
Polystyrene
CH
3
Cl
CH
3
n
Cl Cl Cl Cl Cl Cl Cl
Vinyl Chloride
Poly(vinyl chloride)
F
2
C CF
2
Tetrafluoroethylene
F
3
C
F
2
C
C
F
2
F
2
C
C
F
2
F
2
C
C
F
2
F
2
C
C
F
2
F
2
C
C
F
2
F
2
C
C
F
2
CF
3
n
Poly(tetrafluoroethylene): Teflon
Polyesters, Amides, and Urethanes
Monomer Polymer
CO
2
H HO
2
C
HO
OH
O O
HO O
H
2
C
H
2
C O
n
Terephthalic
Ethylene
Poly(ethylene terephthalate
H
E t
p
acid glycol Ester
HO OH
O O
4
H
2
N NH
2
4
Adipic Acid 1,6-Diaminohexane
Nylon 6,6
HO N
H
N
H
H
O O
4 4
n
CO
2
H HO
2
C NH
2
H
2
N
Kevlar
O
HO
O
H
N
H
N H
n
Amide
4
Terephthalic
acid
1,4-Diamino
benzene
Kevlar n
HO
OH
Ethylene
glycol
H
2
C OCN NCO
4,4-diisocyantophenylmethane
Spandex
H
2
C
H
N
H
N
O
HO
O
O
H
2
C
H
2
C O H
n
Urethane linkage
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Natural Polymers
Monomer Polymer
Isoprene
n
Polyisoprene:
Natural rubber n Natural rubber
O
H
HO
H
HO
H
H
OH
H
OH
OH
Poly(-D-glycoside):
cellulose
O
H
O
H
HO
H
H
OH
H
OH
OH
H
n
-D-glucose
H
3
N
O
O
Polyamino acid:
H
3
N
O
H
N
R
O
H
N
R
O
OH
R n
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R
protein
R
1
R
n+1
R
n+2
n
Amino Acid
Base
O
OH
O P
O
O
O
oligonucleic acid
DNA
Nucleotide
Base =C, G, T, A
Base
O
O
O P
O
O
O
DNA
DNA
What Makes Polymers Unique?
Really big molecules (macromolecules) like
polymers have very different properties than
small molecules small molecules
Chain entanglement: Long
polymer chains get entangled with
each other.
When the polymer is melted, the
chains can flow past each other.
Below the melting point, the chains
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can move, but only slowly. Thus the
plastic is flexible, but cannot be
easily stretched.
Below the glass transition point, the
chains become locked and the
polymer is rigid
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Physical Properties
Stretch
Linear Polymer
Stretch
The chains can be stretched, which causes
them to flow past each other. When released,
the polymer will not return to its original form.
Cross-Linked Polymer
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Stretch
The cross-links hold the chains together.
When released, the polymer will return to it's
original form.
Relax
Polymerization Processes
Addition Polymerization
No Byproducts
Usually heat driven Usually heat driven
Condensation Polymerization
Byproducts produced
Removal of byproduct controls rate
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Polymer Synthesis
There are two major classes of polymer formation
h i mechanisms
1. Addition polymerization: The polymer
grows by sequential addition of monomers to a
reactive site
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Chain growth is linear
Maximum molecular weight is obtained early
in the reaction
Polymer Synthesis
2. Step-Growth polymerization: Monomers p p y
react together to make small oligomers. Small
oligomers make bigger ones, and big
oligomers react to give polymers.
Chain growth is exponential
Maximum molecular weight is obtained late
10
g
in the reaction
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Anatomy of Addition Polymerizations
Initiation
Generation of active initiator
Type of Initiator: Type of Initiator:
Azo (-N=N-)
Disulphide (-S-S)
Peroxide (-O-O)
Example :
B l P id
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Benzoyl Peroxide
AIBN
Reaction with monomer to form growing
chains
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Anatomy of Addition Polymerizations
Propagation
Chain extension by incremental monomer
addition addition
Chain Termination
Conversion of active growing chains to inert
polymer
Combination or disproportionation
Chain Transfer :Transfer of active growing
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Chain Transfer :Transfer of active growing
site by terminating one chain and reinitiating a
new chain.
Chain transfer to monomer, to solvent and to
polymer
Addition Polymerization
In*
A
Initiation
In A* A
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Addition Polymerization
Propagation
In*
A
Initiation
In A A* A
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Addition Polymerization
Propagation
A In*
A
Initiation
In A A A*
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Addition Polymerization
Propagation
nA
In A A A A
n
A*
*A A A A A
In*
A
Initiation
In A A A A*
A A A A A
m
In A A A A
n
A
*A A A A A
m
Combination
*A A A A A
m
In A A A A
n
A
B A A A A
m
Disproportionation
T i ti
A
In A A A A
n
A
A*
Chain Transfer
New reactive site
is produced
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Termination
Reactive site is consumed
MW
k
propagation
k
ter mination
MW
% conversion
0 100
Types of Addition Polymerizations
Ph
Anionic
C
3
H
7
Li
C
4
H
9
Li
+
Ph
n
C
4
H
9
Ph Ph
Li
+
n
Ph Ph Ph
Ph
Radical
PhCO
2

Ph
n
Cationic
PhCO
2
Ph
PhCO
2
Ph Ph
n
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Ph
Cl
3
Al OH
2
H
Ph
HOAlCl
3
Ph
n
H
Ph Ph
n
HOAlCl
3
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20
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Branching: High and low density
Polyethylene
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Commodity Polyolefins
Polyethylene
High Density (1954)
HDPE
Low Density (1939-1945)
LDPE
P k i Fil i d bl ti t fl ibl
HDPE
Bottles, drums, pipe, conduit, sheet, film
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Packaging Film, wire and cable coating, toys, flexible
bottles, house wares, coatings
Linear Low Density (1975)
Shirt bags, high strength films LLDE
BRANCHING OF POLYMER CHAINS
55%
85-95%
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Commodity Polyolefins
Polypropylene (1954) yp py ( )
PP
dishwasher safe plastic ware, carpet yarn, fibers and ropes,
webbing, auto parts
Polyisobutylene (1940)
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Polyisobutylene (1940)
PIB
inner tubes, flexible adhesives, raincoats
Commodity Vinyl Polymers
Polystyrene (1920) y y ( )
PS
Styrofoam, clear plastic cups
envelop windows, toys
Poly(vinyl chloride) (1927)
Cl
Cl
Cl Cl
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Poly(vinyl chloride) (1927)
PVC
garden hose, pipe, car trim, seat covers, records,
floor tiles
Cl Cl Cl
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Semi-Commodity Polymers
Poly(methyl methacrylate) (1931)
CO
2
CH
3
CO
2
CH
3
CO
2
CH
3
CO
2
CH
3
CO
2
CH
3
y( y y ) ( )
PMMA
plexiglas, embedding resin, resist for X-ray applications
2 3 2 3
F
F F
F
F
F
F
F
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Polytetrafluoroethylene. (1943)
teflon, non stick cookware, no grease bearings,
pipe-seal tape
F
F
F
F
F
F
F
F
Step-Growth Polymerization
Stage 1
Consumption
of monomer
n n
Stage 2
Combination
of small fragments
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Stage 3
Reaction of
oligomers to give
high molecular
weight polymer
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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 not obtained unless high conversion of monomer
is achieved.
X
n

1
1 p
100
1000
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X
n
= Degree of polymerization
p =mole fraction monomer
conversion
1
10
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction Conversion (p)
Nylon-6,6
Cl Cl
O O
4
H
2
N NH
2
4
Adipoyl chloride 1,6-Diaminohexane
Cl N
H
N
H
H
O O
4
4
NaOH
HO N
H
N
H
H
O O
4 4
n
6 carbon 6 carbon
Adipoyl chloride
in hexane
Nylon 6,6
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6 carbon
diacid
6 carbon
diamine
Nylon-6,6
Diamine, NaOH, in H
2
O
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Nylon-6,6
Since the reactants are in different
phases, they can only react at the
phase boundary. Once a layer of
polymer forms, no more reaction
R i th l ll
Adipoyl chloride
in hexane
Nylon 6,6
occurs. Removing the polymer allows
more reaction to occur.
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Diamine, NaOH, in H
2
O
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Condensation Reaction
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Commodity Condensation Polymers
N
C
H
O
N
N
C
C
O H
Nylon 6 /
bearings, molded parts
carpet yarn
marine rope
cooking/boiling bags
Nylon 66 (1939)
Fibers, tire cord, fishing line
H
O H
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g g g
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Commodity Condensation Polymers
O
O
C
C
O
Polyester (1941)
PET, dacron, mylar, kodel
fibers, film-backing, magnetic tapes, soft drink bottles, tire
cord, moldings
P l b t (1957)
O
O
O
O
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Polycarbonate (1957)
PC, Lexan
shatter proof glass, cd-disks, car doors and roofs,
appliance housings
O
Polymer Categories: Price
Commodity <$1/pound
E i i $1 5 $5/ d Engineering $1.5-$5/pound
Specialty >$5/pound
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Semicrystalline Thermoplastic
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Crystalline Structures
Single Crystals Single Crystals Polymer Polymer Spherulites Spherulites
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Sharmistha Sharmistha Datta Datta & David J. W. Grant, & David J. W. Grant, Nature Reviews Drug Discovery Nature Reviews Drug Discovery 3, 3,
42 42--57 (January 2004) 57 (January 2004)
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Two crystalline morphologies
(collections of lamellar crystalites)
Spherulite (no shear) Spherulite (no shear)
Row Nucleated (shear )
Shish-kebab
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Polymer Categories: Network
Thermoset vs Thermoplastic
Network vs Linear
Fixed vs Reshapeable
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