Which Materials Are Polymers?

Naturally Occurring Engineering Polymers

• Wood
• Rubber
• Leather
• Cotton, Wool, Silk
Synthetic Engineering Polymers
• Polyethylene (Squeeze Bottle)
• Polyester (‘60’s Fabric), Polypropylene (‘80’s Fabric)
• Polystyrene (Styrofoam, Blue Insulation)
• Polyvinylchloride (PVC - plastic pipes)
• Polytetrafluoroethylene (Teflon, Gortex)
• Polymet hylmet hacrylate (Plexiglass)
• Polyhexamethylene adipami de (Nylon 6,6)

What’s a Polymer?
Material composed of long chain molecules in which a like
unit (“monomer”) is repeated along the chain
• Classi c Example: Polyethylene
• Characteri sti c Features: -C-C-C-”Backbone wi th Atoms or Molecules
Sti cki ng off the si des

H H H H H H
C C ... C C C C ...
H H H H H H
...
...

Ethylene Polyethylene

"Monomer" "Polymer"

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 Hydrocarbon molecules (I)
• Most polymers are organic, and for med from hydrocar bon
molecules
• Each C atom has four e- that participate in bonds, each H
atom has one bonding e-

Hydrocarbon molecules (II)

Double and triple bonds can exist between C atoms
(sharing of two or three electron pairs).
These bonds are called
unsaturated bonds.
Unsaturated molecules
are more reactive.

• Bifunctional Mer units have 2 active bonds to connect

with other mers (Polyethylene).
• Trifunctional Mer units have 3 active bonds to connect
with other mers.
They for m three dimensional molecular network
structures (Phenol-for maldehyde).
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 Isomers
Definition: 1. Molecules with the Same Composition, but
Different Molecular Structure
2. Isomers are molecules that contain the same
atoms but in a different arrangement.
H
• Example: Butane (C4H10) HC H
H H H H H H
H C C C C H H C C C H
H H H H H H H

Butane Isobutane

Physical properties may depend on Isomeric state

(e.g. boiling temperature of nor mal butane is -0.5oC,
of isobutane -12oC)
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Polymer molecules
• Polymer molecules are very large: macromolecules
• Most polymers consist of long and flexible chains with a
string of C atoms as a backbone.
• Side-bonding of C atoms to H atoms or radicals
• Double bonds possible in both chain and side bonds
• Repeat unit in a polymer chain (“unit cell”) is a mer
• A single mer is called a monomer

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To Make Polymers of Different Composition
Add/Change t he Radicals (= “Side Groups”)
• -R is a Group of Atoms that Remain Single Units
During Chemical Reactions (i.e., they don’t react
during chain for mation
H H H H H R H R
... C ... ... C C C C ...
C C C
H H H H H H H H

H H
HCH HCH H H H
... C C ...
H H H Cl H Cl C C
... C ... ... C C C C ... H H H
C C C
H H H H H H H H

Polypropylene Polyvinyl chloride Polystyrene

R = CH3 R = Cl R = C6 H5

Some Common Polymers

(Plexiglass)

(Teflon)

(“Bakelite”)

(for Styrofoa m)

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 Some Common Polymers (II)

Polymerization
(How to Make Polymers from Monomers)
Two Basic Mechanisms
• Addi ti on Reacti ons
• Condensati on Reacti ons
Example: Condensation Reaction ( Polyester! )

Functional Groups REACT Chemically

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 Polymerization (II)
• Ethylene (C2H4 ) is a gas at room temperature and pressure.
• Ethylene transfor m to polyethylene (solid) by for ming active
mer through reaction with initiator or catalytic radical (R.).

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Molecular structure (Types of Polymers)

1 Linear polymers: Van der Waals bonding between chains.
Examples: polyethylene, nylon.

2 Branched polymers: Chain packing efficiency is reduced

compared to linear polymers - lower density

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 Molecular structure (II)
3 Cross-linked polymers: Chains are
connected by covalent bonds. Often
achieved by adding atoms or molecules
that form covalent links between chains.
Many rubbers have this structure.
4 Network polymers: 3D networks made
from trifunctional mers.
Examples: epoxies, phenolfor maldehyde

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Possible Shape(s) of Polyethylene Chains

Carbon Backbone
• Group IV ⇒ Likes
109o Bond Angles Idealized Drawing

(Regular Pattern)
(Irregular Pattern)

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 Summary Chart for Molecular
Characteristics

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Crystal Structure
Triclinic Unit Cell
of Nylon 6,6 Polyethylene

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 Polymer Crystals
Thin crystalline platelets grown from solution - chains fold
back and forth: chain-folded model

The average chain lengt h is much greater than the thickness

of the crystallite 17

Semicrystalline Polymers
Spherulites:
Aggregat es of
lamellar crystallites
~ 10 nm thick,
separated by
amorphous material.
Aggregat es
approxi mately
spherical in shape.

Photomicrograph of
spherulite structure
of polyethylene 18

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 Polymer Crystallinity (I)
Atomi c arrangement
i n polymer crystals
i s more complex
than i n metals or
cerami cs (uni t cells
are typi cally large
and complex).

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Polymer Crystallinity (II)

Polymer molecules are often partially crystalline
(semicrystalline), with crystalline
regions dispersed within
amorphous material.

More crystallinity:
higher density, more strengt h, higher
resistance to dissolution and softening by heating

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 Polymer Crystallinity (III)
Crystalline polymers are denser than amorphous
polymers, so the degree of crystallinity can be
obtained from t he measurement of density:

rc: Density of perfect crystalline polymer

ra: Density of complet ely amor phous polymer
rs: Density of partially crystalline polymer that we are
analyzing

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