Polymers and Polymerization in

Dentistry
Dr Amal Ezzeldin Fahmy
Assistant Professor of Dental Biomaterials Faculty Of
Dentistry Alexandria University

DR Amal Ezz EL Din

 What is the lecture about ?

• • Terms and definitions[monomer-

polymer]
• • Structure of polymer chains
• • Applications of Polymers in dentistry
• • Polymerization reactions classification
• • Methyl methacrylate polymers

DR Amal Ezz EL Din

 Terminology
•Monomer + monomer = polymer
•Monomer1 + monomer2 = copolymer
•Oligomonomer= 2-4 monomers

– Poly = many
– Mono = single
– Mer = unit
– Oligo =several

DR Amal Ezz EL Din

 Definitions
• Monomer
• MONO = ONE
• MER = PART
• A monomer is the simplest
repeating structure unit
(molecule) which join
together to form a polymer
• Ethylene to give
polyethylene
• Methyl methacrylate to give
poly methyl acrylate
• Polymer – a chemical
compound consisting
• of giant molecules
„MACROMOLECULES“
• formed by union of many
„POLY“ small repeating units
„mers“
MONO“MER“ molecules to form
POLY“MER“ chain,
macromolecule

DR Amal Ezz EL Din

 H H H H H
C C C C C
H H H H H

Ethylene
POLY
Ethylene

DR Amal Ezz EL Din

DR Amal Ezz EL Din
 Definition of Polymerization
• The process by which low mol. Wt
compounds called monomers combine to
form high mol. Wt . polymers
• It requires the presence of covalent bonds
in the monomer

DR Amal Ezz EL Din

 Applications of Polymers in Dentistry

• Denture base materials

• ·Acrylic teeth(Artificial)

DR Amal Ezz EL Din

 Applications of Polymers in
Dentistry
• Soft Linings:
plasticised
polymers, higher
methacrylates and
silicone rubbers.

DR Amal Ezz EL Din

 Applications of Polymers in Dentistry
• Cements: polyacrylic acid is a constituent of zinc
polycarboxylate cements and glass-ionomer
cements.
• ·

• ·
• Polymeric crown and bridge materials
•
• Die materials: filled polymer

DR Amal Ezz EL Din

Applications of Polymers in Dentistry
cont.

Removable tooth
movement devices

Orthodontic retainers

DR Amal Ezz EL Din

Applications of Polymers in Dentistry

Impression
materials:
e.g
agar and alginates
polysulphide,
silicone
polyether elastomers

DR Amal Ezz EL Din

 Applications of Polymers in
Dentistry
• Mouth guards
(Athletic mouth
protectors)

DR Amal Ezz EL Din

 Applications of Polymers in Dentistry

• Restorative materials:
composite materials
• Polymers used in the
so-called adhesive
techniques
• natural resins such as
copal or rosin
Varnishes contain

DR Amal Ezz EL Din

 Types of polymers based on their nature

• Natural polymers eg proteins, agar alginate

,starch,DNA .
• Synthetic polymers as nylon ,terylene,vinyl
polymers PVC ,polystyrene ,polyethylene,
polypropylene

DR Amal Ezz EL Din

 Structure of polymers based on spatial
arrangement of monomer molecules
• Three basic structures:
• Linear
• Branched
• Cross-linked

DR Amal Ezz EL Din

 Structure of Polymers

In the branched polymers There are side

DR Amal Ezz EL Din
chains
Structure of polymers

DR Amal Ezz EL Din

 Cross-linkage
• It provides a sufficient number of bridges
between linear macromolecules to form a
three dimensional network that alter
strength ,solubility ,and water sorption

DR Amal Ezz EL Din

DR Amal Ezz EL Din
 Cross Linking
• Increases hardness and stiffness (increases
mol.wt)

• Increases crazing resistance (small cracks

originating at the teeth-denture margin),
wear and solvent resistance, but increases
brittleness

• - Increases thermal resistance (polymers are

easily finished - grinded and polished but
without melting.

• Decrease water sorption and solubility.

DR Amal Ezz EL Din
 Based on the type of polymerization reaction

• I-ADDITION POLYMERIZATION
• II-CONDENSATION POLYMERIZATION

DR Amal Ezz EL Din

•Addition polymerisation:
– No by products
– Polymer mwt = Σ mwt monomers
•Condensation polymerisation:
– By products are produced and lost in the
final product
– Polymer mwt ≠ Σ mwt monomers

DR Amal Ezz EL Din

 Types of Addition Polymerization
• Types of addition polymerizations:
• 1• Free-radical polymerization active center is a
radical (contains unpaired electron) and the
propagating site of reactivity is a carbon radical.
There must be unsaturated carbon –carbon double
bond
• 2•Ring opening polymerization
• 3• Ionic polymerization

DR Amal Ezz EL Din

 Stages of Free Radical addition
polymerization
• Free Radical Polymerization
• Most free radical polymerizations involve 3-steps:
• 1. Initiation : to get things started (formation of free radicals ) free radical react
with C=C of the monomer to grow the polymer
•
• 2. Propagation : linking of more monomer units to form polymer units
(theoretically all monomer units should react
however polymerization is never fully completed.
• 3. Termination : to end the reaction
NB:A Free radical is a molecular fragment with an unpaired electron usually
BENZOYL PEROXIDE is most commonly used in dentistry
It can be activated by heat ,chemical reaction or by light

DR Amal Ezz EL Din

 Stages of Addition polymerization

• Initiation
• R1 ˙ + M R1M˙
• Propagation
• R1M˙ + M R1MM˙
• R1MM˙+M R1MMM˙
• Termination
• R1Mn˙ + R1Mm˙ R1Mn+ R1Mm

DR Amal Ezz EL Din

DR Amal Ezz EL Din
DR Amal Ezz EL Din
 Termination
• Takes place by :
• Direct coupling
• Exchange of H atom from one growing chain
to another
• Chain transfer: the activated radical is
converted to an inactive molecule

DR Amal Ezz EL Din

DR Amal Ezz EL Din
 Condensation polymerization
• It is a reaction between two molecules to form a larger
molecule with elimination of a smaller molecule.
• Polymerization is accompanied by repeated elimination of
small molecules e.g. water ,halogen, alcohol.
• Examples:
• Poly sulphide rubber (water is a by-product)
• Condensation silicone (ethyl alcohol is a by product)

DR Amal Ezz EL Din

Polysulphide impression setting rxn

DR Amal Ezz EL Din

Condensation silicone

DR Amal Ezz EL Din

 Copolymerization
• It can be defined as the reaction between 2 or more
chemically different monomers each having some
desirable property:

DR Amal Ezz EL Din

 Types
Random :A-B-B-B-
A-B-A
Alternating : A-B-A-
B-A-B

Block: A-A-B-B-A-A-
B-B
Graft: A-A-A-A-A
B B

DR Amal Ezz EL Din

DR Amal Ezz EL Din
 Plasticizers
• They are substances
added to the resins :
• 1-To increase the
solubility of the
polymer in the
monomer
• 2-To decrease the
brittleness of the
polymer
• 3-It also decrease
strength hardness and
softening temperature
e.g. dibutyl phthalate

DR Amal Ezz EL Din

 Plasticizers effects
•Added to stiff, glassy uncross-linked polymers
•Lowers glass transition temperature (Tg)
•Become
– rubber-like,
– Flexible
– less brittle

DR Amal Ezz EL Din

 Different classifications of polymers

• Based on the nature of polymers

• Based on the spatial arrangement of
monomer molecules
• Based on thermal behavior
(,thermoplastic, thermoset)
• Based on the type of polymerization
reaction (addition & condensation )
• Based on the chemical compostion
(homopolymer &copolymer)
DR Amal Ezz EL Din
 Types of polymers according to their thermal behavior

• Thermoplastic: Polymers that can be molded without chemical

change they flow and soften when heated and pressed; thus,
easily shaped .They are soluble in organic solvents and are
fusible.
(polyethylene, polyvinylchloride) these can be molded by a physical
change e.g change in temperature

• – Thermosetting: Decomposed when heated; thus, can

not be reformed or recycled. Presence of extensive
Cross links between long chains induce decomposition
upon heating and renders thermosetting polymers
brittle. (epoxy and polyesters) A chemical reaction takes place
during the molding process and the final product is chemically
different than the original substance
They are insoluble and infusible

DR Amal Ezz EL Din

 Polymerization can be INHIBITED (prevented)
by:
• Adding impurities e.g: hydroquinone which react with the
activated nucleus or with an activated growing chain to
prevent further polymerization
• Presence of oxygen retards polymerization as it react with
the free radicals
• water

DR Amal Ezz EL Din

 Why inhibitors are added?
• 1. To extend monomer shelf life by
• restricting spontaneous polymerization
• 2. Decrease sensitivity to ambient light
• 3. To prolong working time

DR Amal Ezz EL Din

 Types of polymers
• Elastomers:
• They are polymers which can be stretched in a
manner similar to rubber and will relax to their
original dimensions when unstressed

• Can undergo extensive elastic deformation (natural

rubber, silicone)

DR Amal Ezz EL Din

 Acrylic plastics for Denture Bases
• Powder-liquid type • Liquid =MMA
most popular – Highly volatile
• Polymer= PMMA – Always supplied in a
– Principle component dark bottle
of powder – BP=100.3
– Present as beads or – Immiscible in water
pearls – Highly flammable
• Wide range of
shades available

DR Amal Ezz EL Din

H CH3
H CH3
C= C C=C
H COOH H COOCH3

Methyl
Methyl Acrylic acid Methacrylate

DR Amal Ezz EL Din

 Acrylic denture base polymer
• Presentation: - powder-liquid
- gels
- sheets or blanks

DR Amal Ezz EL Din

Processing

DR Amal Ezz EL Din

THANK YOU
DR Amal Ezz EL Din
DR Amal Ezz EL Din
• Another example for
free radical addition
polymerization
responsible for
setting of composite
resins

O CH3 O
CH2=C-C-O-CH2CH-CH2O -C- OCH2CHCH2O-C-C=CH2
CH3 OH CH3 OH CH3

Bis GMA
DR Amal Ezz EL Din
 RING OPENING
POLYMERIZATION
Working
Cast with
• The ring structure is the Removable
structure is opened and cross Dies
linking occur
• e.g. polymerization of
polyethylene rubber base
impression materials it
involves opening of ethylene
imine ring
• Epoxy resins used to form
Edentulous Orthodontic Working
polymeric dies Cast Model Cast
O
CH2_CH2 Removable
Die with
Waxed Inlay

DR Amal Ezz EL Din

 Ionic polymerization
• Here the catalyst brings about the exchange of ions
resulting in a cross linked polymer

• Example : addition silicone impression materials

• Vinyl terminated polydimethyl siloxane+ silane
terminated siloxane HPTCL silicone rubber

DR Amal Ezz EL Din

DR Amal Ezz EL Din
 H CH
C= C
H COOH

ethylene acrylic acid

DR Amal Ezz EL Din