POLYMERS

Introduction to Polymers
.
You may think of polymers as being a relatively modern
invention however, naturally occurring polymers have been
used for thousands of years.

Ex. wood, rubber, cotton, wool, leather, silk,.. Etc

Artificial polymers are, indeed, relatively recent and mostly

date from after WWII.

in many cases, the artificial material is both better and

cheaper than the natural alternative

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 INTRODUCTION TO POLYMERS

styrofoam cups, contact lenses, rubber tires, telephone

housings, epoxies, sandwich bags, soda bottles, rubber
bands, computer keyboard keys, cables etc

in fact, just look around your, house, dorm or apartment room

and youll likely find plenty of examples of polymeric
materials.

COMMERCIAL Polymers: used in large quantities for their

lightweight, corrosion-resistance, and good formability.
- usually low strength and stiffness

ENGINEERING Polymers: improved strength and

better elevated temperature properties.
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Different aspects of polymer science:
Polymer synthesis
Polymer characterization
Polymer physical chemistry
Paul J. Flory, Nobel prize for chemistry, 1974
Polymer physics
Pierre de Gennes, Nobel prize for physics, 1991
Polymer engineering

Each of these aspects has considerable industrial and

research significance. The successful polymer
scientist has some understanding of all of these
areas.
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 DEFINITIONS:

Polymer: long molecule made up by the repetition of

small units
Synonym: macromolecule
High molecular weight (M)
Ex. polystyrene (PS)

Monomer: molecule that combines with others

(identical or different) to form a polymer
Ex. ethylene (PE polyethylene)

Oligomer: low molecular weight polymer, constituted

of at least two monomers
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 CLASSIFICATION OF POLYMERS

1. Thermoplastics:
Can be processed by melting and cooling.
- several cycles are possible for thermally stabilized polymers
Ex. PS, PE, PP, PVC, PET
PP

PVC

PET

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 CLASSIFICATION OF POLYMERS

2. Thermosets:
Cannot be melted or dissolved to be processed; chemical
decomposition occurs before softening.

3. Rubber (Elastomers)
Ex. Styrene-butadiene

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 MOLECULAR FORCES IN POLYMERS

Intramolecular forces: forces between atoms in one chain

covalent bonds (strong)

Intermolecular forces: forces between two polymer chains

Van der Waals forces
- present in non-polar hydrocarbon polymers like PE, PP, etc.

hydrogen bridges
- stronger than VW
- present in polar polymers like poly amides and polyester

- Whether polar or nonpolar IMFA can become very strong as

MW increases.

Entanglements (physical interaction)

- In the crystalline state the Van der Waals bonds are very important.
- In the rubbery amorphous state the entanglements are very important.
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 MOLECULAR SHAPE

The polymer chain can bend, twist, and kink into many shapes.

Adjacent molecules can intertwine leading to the highly elastic

nature of many polymers, such as rubber.

Random kinks and coils lead to entanglement, like in the

spaghetti structure:

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Structural properties of
linear polymers:
1. conformational flexibility
2. strength

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Cross linking adds
tensile strength

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 BASIC POLYMER STRUCTURE

Suppose our repeating unit is an X. Then, a linear polymer

based on X would look like the following:

--X--X--X--X--X--X--X--X--X--X--X--X

-where each X represents a mer.

-Sometimes, polymers contain functional side groups, called
pendant groups (Y):

-We call the primary linear chain the backbone

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 HOMOPOLYMERS AND CO-POLYMERS

Homopolymer = If only one type of monomer is present.

co-Polymer = If a second monomer is also present in the chain.

Model for a homopolymer: --X--X--X--X--X--X--X--X--X--X--XX

Model for an alternating co-polymer:

--X--W--X--W--X--W--X--W--X--W--XW

Model for random co-polymer:

-X--X--X--W--X--W--X--XW--X--W-W

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Model for graft co-polymer:
A polymer is grafted to another preformed macromolecule
ex. Impact resistant PS branches on polybutadiene rubber

Model for block co-polymer:

Long segment on one monomer alternates with another long

segment of different monomer.
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--X--X--X--X--XX--W--W--W--W--W--W--
 STRUCTURE OF POLYMERS
Polyethylene: (the mer unit is C2H4)

This is an example of a linear chain homopolymer, where the

X in our model is replaced with the ethylene group.

Polyethylene is used for flexible bottles, toys, battery parts,

ice trays, and film wrapping and other packaging materials.

It is tough but possesses low strength.

Trade names: Ethron, Fortiflex, Hi-fax, Rigidex

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 STRUCTURE OF POLYMERS
Polypropylene: (the mer unit is now -C3H6 , propylene)

Polypropylene is used for such items as bottles, TV cabinets,

luggage.

It tends to be relatively strong and resistant to heat.

It has the trade names Herculon, Meraklon, and Profax.

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 STRUCTURE OF POLYMERS
Polyvinyl chloride: (the mer unit is C2H3Cl)

Polyvinyl chloride is a very popular, low cost rigid material

It can be made flexible by adding plasticizers.

It is used as floor coverings, pipe, garden hose, electrical

wire insulation, and (at one time) phonograph records.

Tradenames: PVC, Saran, Tygon, Darvic, Geon.

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 SYNTHETIC AND BIOLOGICAL POLYMERS

Polymers are classified as:

(1) Man-made or synthetic polymers that are synthesized in

the laboratory;

(2) Biological polymer that are found in nature.

Synthetic polymers: nylon, poly-ethylene, poly-styrene

Biological polymers: DNA, proteins, carbohydrates

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 METHODS FOR MAKING POLYMERS
1. Addition polymerization
2. Condensation polymerization

Addition polymerization: monomers react to form a

polymer without net loss of atoms.

Most common form: free radical chain reaction of

ethylenes

n monomers one polymer molecule

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Example of addition polymers

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Free-Radical Addition Polymerization of
Ethylene
H2C CH2

200 C O2
2000 atm peroxides

CH2 CH2 CH2 CH2 CH2 CH2 CH2

polyethylene
Free-Radical Polymerization of Propene

H2C CHCH3

CH CH CH CH CH CH CH
CH3 CH3 CH3 CH3 CH3 CH3 CH3

polypropylene
 ..
RO
.. Mechanism
H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3

 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3

H2C CHCH3
 Likewise...

H2C=CHCl polyvinyl chloride

H2C=CHC6H5 polystyrene

F2C=CF2 Teflon
A polymer made
form just one
monomer is
polyethylene. It
is the most
common plastic
you see.
It is used for
bottles, buckets,
jugs, containers,
toys, even
synthetic
lumber, and
many other
things.
 There are two types of
polyethylene polymers
(plastics). One is when
the polyethylene exists as
long straight chains. The
picture here shows the
chains of one carbon with
two hydrogen atoms
repeating. The chain can
be as long as 20,000
carbons to 35,000
carbons. This is called
high density polyethylene
(HDPE).
 When the chains get up to
500,000 carbons long, they
are tough enough for
synthetic ice, replacement
joints, and bullet-proof vests.
Think about it. You start
with ethylene gas molecules
that can't stop a feather from
passing through them. But
after the double-bond of one
ethylene molecule breaks, it
causes a chain reaction that
connects thousands to it. In
less than a second, these
long straight chains of
carbon and hydrogen are
strong enough to stop a
bullet or play ice hockey on.
Isn't chemistry wonderful.
We've mentioned high density polyethylene (HDPE); you
probably were thinking, there must be low density polyethylene
(LDPE). You are correct. It is made by causing the long chains
of ethylene to branch. That way they cannot lie next each
other, which reduces the density and strength of the
polyethylene. This makes the plastic lighter and more flexible.
Low density polyethylene is used to make
plastic bags, plastic wrap, and squeeze bottles,
plus many other things.
Another polymer, which is almost the same as
polyethylene, is PolyVinyl Chloride or PVC.
The difference is that every other hydrogen is
replaced with a chlorine atom (green sphere).
(CH2CHCl)n + O2 CO2 + CO + HCl + H2O
PVC pipes are used in our homes
and they are even handy for making
a table or chair. PVC is also used as
insulation around electric wires in the
home and the automobile. PVC is
quite safe until it burns. The
chlorines in the PVC combine with
the hydrogen atoms in the PVC to
form hydrogen chloride gas (HCl).
When this contacts water in lungs or
mouth, it turns to hydrochloric acid
(HCl(aq)).
There are many types of plastics, but they all are based on taking one or two
small molecules and starting a chain reaction that connects hundreds or
thousands of these small molecules into long chains or branching chains. By
controlling the length and the branching, you can control the final hardness
or flexibility of the polymer plus qualities like resistance to solvents, acids, or
heat.
 Condensation polymerization

Condensation polymerization: the polymer grows from

monomers by splitting off a small molecule such as
water or carbon dioxide.

Example: formation of amide links and loss of water

Monomers

First unit of polymer + H2O

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Rembember from GChem?

Nylon is a condensation polymer

made of the monomers adipic acid
and hexamethylene diamine.

O OH
O

OH
Q uickTim e and a
Phot o - JPEG decom pr essor
ar e needed t o see t his pict ur e.

They're nylons, Benjam

adipic acid
+
NH2
H2N

hexamethylene diamine

nylon

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Nylon is used in clothes,
shoes, jackets, belts, and
accessories. Its not
surprising a magazine is
named after this polymer.
Where did nylon get its
name?

Nylon was discovered in 1935. The name nylon is

derived from two cities where it was discovered namely
New York (NY) and London (LON).
 Two ingredients are mixed and a solid begins to form
at the junction between the two layers of liquid.

Hot nylon spaghetti can be extracted.

We say certain polymers are man-made, but the truth is they

make themselves. Humans only have to get the ingredients
near each other. The chemicals will assemble themselves.
The students are handling the nylon string that was produced.
Notice theres some kind of odor that is being noticed.
 Tetramethylene
dicarboxylic acid Hexamethylene diamine
(adipic acid)

methylene x 6 (hexa) amine x 2 (di)

Nylon is actually a copolymer because is it made

from two monomers. When these two monomers
are in the same beaker, they combine and give off
a molecule of water. This is called a dehydration
reaction because we are taking away (de) water
(hydra). (regarding odor: amines smell like fish or
worse. Adipic acid is odorless )
 Hydrogen bonds between chains

Supramolecular
Structure of
nylon

Intermolecular
hydrogen bonds
give nylon
enormous tensile
strength

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 Polyester is a
another
copolymer. It
is made from
equal amounts
of two different
monomers.
Polyester is
used to make
bottles and
fabrics.
Polyester is made from the two monomers, terephthalic acid (note: ph is
silent) and ethylene glycol (car antifreeze). This makes a popular plastic
called PETE, which is short for Polyethylene Terephthalate. The synthesis
is also a dehydration reaction because water is given off.

PETE

O
H O C

ESTER groups formed Hence the name POLYESTER

 Biopolymers

Nucleic acid polymers (DNA, RNA)

Amino acids polymers (Proteins)

Sugar polymers (Carbohydrates)

Genetic information for the cell: DNA

Structural strength and catalysis: Proteins

Energy source: Carbohydrates

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 Proteins: amino acid monomers

The basic structure of an amino acid monomer

HO NH2
H
O R

The difference between amino acids is the R group

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 Proteins: condensation polymers

Formed by condensation polymerization of amino acids

Monomers: 20 essential amino acids

NH2 General structure of an amino acid
H R
CO2H R is the only variable group

Glycine (R = H) + Glycine First step toward poly(glycine)

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Representation of the
constitution of a protein

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Three D representation of the structure of a protein

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DNA
 Thymine (T)
The monomers:

Adenine (A)
Cytosine (C)

Guanine (G)

Phosphate-
Sugar (backbone) of
DNA
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Phosphate-
sugar
backbone
holds the DNA
macromolecule
together

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One strand
unwinds to
duplicate its
complement via a
polymerization of
the monomers
C, G, A and T

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Carbohydrates
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Cotton fiber is mostly cellulose, and
cellulose is made of chains of the sugar,
glucose linked together a certain way.
 Glucose Glucose
Two ring-shape
Structural formula.
versions
Straight chain
glucose
H-C=O
1 Glucose Used in
glucose bending making
|2 starch
H-C-OH
|
3 flips
HO-C-H either
| bends way
4 alpha-glucose
H-C-OH
|5
H-C-OH
|6 Used in
CH2OH making
cellulose
Glucose bends itself into 4
different shapes millions of
times a second beta-glucose
 POLYMER ADDITIVES
Mechanical, chemical, and physical Properties can be modified by
additives:

Fillers
Improve tensile and compressive strengths, abrasion resistance,
toughness, and thermal stability
sand, glass, clay, talc (eg. carbon in tires)
Particle sizes range from very small (10 nm) to large (mm)

Plasticizers
small molecules which occupy positions between polymer chains hence
increase distance and interactions between chains.
increases flexibility, ductility, and toughness
reduces hardness and stiffness

Stabilizers
UV resistance of C-C bonds
Oxidation resistance
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Colorants and Flame Retardants
 POLYMER RECYCLING

a. Durability of polymer property

1) Advantage : Good materials for use

2) Disadvantage : Environmental problem

b. Treatment of waste polymer : Incinerate,

Landfill, Recycling

ex) Waste Tire : Paving materials

Waste PET : To make monomer ( hydrolysis )
To make polyol ( glycolysis )
The favorite properties of plastics are that they are inert and won't
react with what is stored in them. They also are durable and won't
easily decay, dissolve, or break apart. These are great qualities
for things you keep, but when you throw them away, they won't
decompose.
Since they dont decompose, the answer is to recycle
the plastics so they can be remade into something
else. Here we see a bunch of CDs getting recycled.
The decks, fence, stepping stones, house shingles, and the
sweat shirt, were all made from recycled plastic.
The mile long boardwalk at Yellowstone National
Park was made from recycled plastic.