POLYMERS

Polymers Are long chain molecules consisting

of many (poly) repeating units (mers).
A monomer: Is the smallest repeating unit in
the polymer
Polymerization : Is the chemical reaction by
which polymers are formed from monomers
chain e.g. ethylene monomer.

CLASSIFICATIONS OF POLYMERS
Classifications
according to

Origin

Thermal

Spatial

Polymerization
reaction

The origin

Natural polymers
Agar, cellulose
DNA, proteins
Natural rubber
Collagen and silk

A) Synthetic Polymers
Produced in the laboratory by chemical
reactions. e.g. Acrylic resin ,nylon and
polystyrene.
Originally the synthetic polymers regarded as
substitutes for existing natural polymers such
as rubber and silk .Nowadays a polymers can
be produced and have medical use such as
dialysis and dental application such as filling
materials .

B) Natural Polymers
Proteins polyamides of polypeptides
polyisoprenes
e.g. rubber and gutta-percha
polysaccharides
e.g. starch , cellulose, agar and alginate .
poly nucleic acids
such as DNA and RNA.

Thermal
a) b) Thermoplastic

B)Thermosetting

According To Thermal Behavior

A) Thermoplastic resin
They are polymers which can be
shaped by heat and after cooling
they maintain their shape the
reaction is reversible and can be
repeated

b) Thermoset polymers
Harden during fabrication (irreversible or chemical
reaction).
Chemical
Soft
hard
reaction
Examples are cross-linked
polymethylmethacrylate, silicons ,and bisphenol
A-diacrylates.

characteristics
The polymer chains are bonded to each other by secondary bonds.
They are relatively soft and their mechanical properties
are sensitive to heat.
They dissolve in the organic solvent, thermosetting polymers
They are converted into a permanent shape
and set by chemical reaction.
They can not be remelted and reformed into another shape but
degrade or decompose up on being heated to high temperature..
Thermoset cannot be fused.
The polymers form network with cross links between them
primary covalent bonds. E.g. PMMA.

According to the basis of structural or spatial configuration

3 Basic Types
Branched
linea
r
copolymer

Copolymer
Simple polymer
Has one type
monomer
homopolymer

Cross-linked
polymer

Homo
OR

OR

Random
Random

Block

graft

(a) Linear polymers

(simple polymer)
This may be homopolymer it has one type of
monomer ,or copolymer, this means that it has
more than one type of monomer,
Homopolymer
block

copolymer, random

b) Branched polymers
This type of polymers show higher strength hardness and
less water sorption than linear polymer .
Branched polymers are either homo or copolymer The
branched copolymer may be random or graft types.
2

Homopolymer

copolymer, random
graft

C) Cross-Linking
Polymer chains are cross - linked or attached by
a cross - linking agent such as glycol
dimethaerylate.
Through primary and small degree of cross linking
will limit the amount of movements of the
polymer chains relative to each other.
So when the material is stressed the deformation
is elastic rather than plastic.

Characteristic
1.
2.

3.

4.

Higher strength and hardness.

Higher resistance to crazing which may
be due to Alcohol drinking or solvents
It is the best type used for construction of
denture base and artificial teeth
Low water sorption

Polymerization:
The chemical reaction by which polymers are prepared from
monomers.
Condensation polymerization
Occurs when two molecules react to form a large molecules
with the elimination of smaller molecule
(Often but not always water)
Addition polymerization
Occurring when a reaction between two molecules
(either the same to form a homopolymer or dissimilar to
form heteropolymer)
produces a large molecule without the elimination of
a smaller molecule such as water

Types of polymerization
Most polymerization reactions are of two types condensation
and addition polymerization.
1)Condensation polymerization:
The reaction between two molecules to form a larger
molecule with the elimination of a smaller such as water
as a by product.
condensation
Polymer + by product
Monomer
polymerization
Example is the polysulphide rubber impression material.

2)Addition polymerization
The reaction between two molecules to give
a larger molecule without the elimination
of a smaller molecule (no by-product).
No change in composition takes place, the
structure of the monomer is repeated many
times in the polymer e.g.
Poly (ethylene), poly (acrylic acid),
polymethacrylic acid) poly (methacrylate).

STAGES OF ADDITION POLYMERIZATION

STAGES OF ADDITION POLYMERIZATION

A
Initiation
Activation and
initiation (by free

B
Propagation

C
Termination

Direct coupling

radical mechanism)
Exchange of a hydrogen atom

A) Activation and initiation

A free radical is a compound with an unpaired
(unshared )electron (very reactive )
The symbol (c= c) represents four electrons the
monomer itself become free radical Benzoyel
peroxide is a substance most commonly used to
generate free radicals before initiation
The activation is done by light, heat or by a chemical
compound such as dimethyl paratoluidine. In this
way the peroxide decomposes giving up free
radicals to initiate the polymerization reaction .

Three stages of addition polymerization Heat

1) Initiation
Amines
C6H5 COOCC6H5

Heat

Amines

2 (C6H5COO) + CO2

Benzoyl peroxide

free radicals (R) + carbon dioxide

CH3
R+ CH2 = C
COOCH3

CH3
R-CH2 C
COOCH3

Free radical + monomer

Free radical activated monomer

B) Propagation
The chain reactions continues with the evolution
of heat until all the monomer has been
changed to a polymer And so on
R1M +M + R1MM + M +R1MMM

R1MN where n is any integral number.

polymer free radical + monomer

growing chain

C) Termination
The reaction terminated either by
a) Direct coupling
This occurs when two free radicals react
to form a stable molecule
1- R1MN + R2MM
R1MN R2MM
b) Exchange of a hydrogen atoms
The chain reactions can be terminated either
by direct coupling or by the exchange of
a hydrogen atom.

Factors associated with polymerization

A) Evolution of heat as the

reactions is strongly exothermic
due to breaking of bonds.
B) Reduction in volume.

Inhibition of polymerization

Any impurity in the monomer which can react

with free Radicals will inhibit or retard the
polymerization reaction
It can react either with the activated initiator
or any activated nucleus or with an activated
growing chain to prevent further growth

The presence of such inhibitors influences the

length of the initiation period, as well as
the degree of polymerization.
The addition of small amount of inhibitor
(Hydroquinone) to the monomer
(Methyl methacrylate)
will inhibit polymerization if no chemical
initiator is present and it will retard the
polymerization in the presence
of an initiator.

Factors affecting the properties of polymers

Many factors affect the properties of polymers

1. Chemical composition of the chain.
2. Degree of polymerization.
3. The number of branches and
4. The cross links between polymer chains.

In general
Longer chains and higher molecular weight polymers
characterized by
(a) Increased strength, hardness Brittleness and
stiffness
(b) Increased resistance to creep.
For example composite resins highly cross- linked
matrix in which large number of strong covalent
linkages between chains transforms the molecules
into a rigid very high molecular weight material
resulting strength, stiffness and withstand occlusal
stresses.

In contrast
Elastomeric impression materials composed of
individual coiled chains with just few cross- links
this type of molecular structure permits the large
scale uncoiling and recoiling of chains that gives
these materials high flexibility.
Two basic properties which characterize polymers
are glass transition temperature (Tg)
and melting temp.
(Tg ) Is the temperature at which the polymer ceases
to be glassy , brittle and become rubber like.

T g = Mw
Molecular weight is another factor which affects
(T g)
The two properties is related by an equation:

Co- polymerization
To modify the properties of the polymer , use two or
more chemically different monomers such as
copolymer process enabled chemists to
tailor make molecules of predicted properties for
special applications e.g.
Addition of sufficient amounts of octyl methacrylate
results in a copolymer that is soft and flexible at
mouth temp.
And that has been used as a soft liner
1. Hydroxyethyl methacrylate increase water sorption
and wetability of the copolymer by saliva .
The material become soft and flexible if placed in
water or saliva It is used as soft contact lenses
and as soft liner for dentures

CROSS-LINKING
Is a chemical bond formed between polymer chains.
A chemical compound with two double bonds per
molecules can act as cross-linking agent since each
C =C bond can react with different chain.
This product has superior properties an example is
ethylene glycol dimethacrylate .
Small degree of cross-linking limits the amount of the
polymer chains when the material is stressed.
The deformation is elastic rather than plastic.
The polymer have high glass transition temperature.
The polymer is harder more brittle and more
resistance to the action of solvents

Plasticizers
Liquids are able to penetrate between the chains of polymer
.The molecules become further apart and the forces
between them become less.
such liquids is called plasticizers
Characteristics
(a ) Soften the material
(b) Make it more flexible by lowering its glass transition
temp . if sufficient plasticizers is added to a polymer It
becomes flexible , rubbery in the mouth below mouth
temperature. So it is used in producing soft lining
materials

Application of polymers in dentistry

Denture base materials.
Artificial teeth.
Tooth restorative
materials.
Cements.
Crown and bridge
facings.
Impression materials.

Dies.
Endodontic fillings.
Mouth protectors.
Maxillofacial prosthesis.
Varnishes,
pit and fissure sealant

THANK YOU