DENTAL POLYMERS

DR HAIDIL
DM
BLOCK 3
OUTLINE
• Intro
• Classification of Polymers
• Stages of Polymerization
• Physical properties of polymers
• References
 Intro and History
• The modern era’s use of dental
polymers began with natural rubber
for dentures.
• Vulcanized rubber,
a plant-derived
latex crosslinked with sulfur, was
introduced as a denture base
material in 1853.
• These materials offered advantages over the wood,
bone, ivory, and ceramics used at the time, but each
also had substantial drawbacks.
• This denture was flexible, allowed easy fabrication of
denture bases, & simulated the look of gingival tissue.
• the celluloid portion absorbed stains, gradually
became grossly discolored, developed odors, and was
flammable. Thus, substantial improvements in both
appearance & functional durability were still needed.
• During the 1890s, gutta-percha, a plant exudate
containing trans-polyisoprene, came into use for
temporary crowns and cavity fillings, permanent
restorations, and root canal (endodontic) filling
materials. Interestingly, gutta-percha,which is closely
related to natural latex rubber (cis-polyisoprene),
remains in wide use as an endodontic material to this
day
• During 20th century a wide variety of synthetic
elastomers—polysulfides, silicone rubber, polyethers,
• During the 1930s and 1940s, phenol-formaldehyde,
polystyrene, polyvinylchloride (PVC), vinyl acetate, and
other synthetic polymers were developed.
• 1936 : PMMA, as a heat-processed thermosetting
material.
• By 1940, PMMA was also being used to make inlays,
crowns, and fixed dental prostheses.
• Mid 1940s, room-temperature polymerizing
methacrylates became available - quickly adapted for
dentistry as self-curing prosthetic and restorative
resins (also known as cold- & chemical-curing resins
 POLYMERS
• Polymers ---origin from Greek ‘polymeros’ ; poly
means many & meros means part.
• A long chain organic molecule consisting of many
repeating units called monomers or mers.
• Example: POLYBUTADIENE = (BUTADIENE+
BUTADIENE+......)n Where n=4,000
• very large molecules made when hundreds of
monomers join together to form long chains.
• complex and giant molecules usually with carbons
building the backbone, different from low molecular
weight compounds.
• The small individual repeating units : monomer
• Imagine that a monomer can be represented by the
letter A. Then a polymer made of that monomer
would have the structure:
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-
• This kind of polymer is known as HOMOPOLYMER
• In another kind of polymer, two different monomers
might be involved.
• If the letters A and B represent those monomers,
then the polymer could be represented as
A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A- B- A
• known as a COPOLYMER

ethylene propylene
Vinyl cholride ------ polyvinylchloride (PVC)

Acrylic acid------ polyacrylic acid

MMA------ PMMA
 DNA
Monomer : Nucleotide
Polymer : Polynucleotide
 CLASSIFICATION OF
POLYMERS

POLYMERS

Spatial Thermal
Origin
Structure Behaviour
1. ORIGIN

Natural polymer : Polymers which are isolated from

natural materials
• E.g. : Cotton, silk, wool, natural rubber

Synthetic polymer : Polymers synthesized from low

molecular weight compounds
• E.g. polyethylene, nylon, terylene. Polyethylene, Acrylic
resin and elastic impression materials
Organic polymer : A Polymer whose backbone chain is
essentially made of carbon atoms
• Examples- cellulose, proteins, polyethylene, nylons.

Inorganic polymer: A Polymer which does not have

carbon atom in their chain
• Examples- Glass and silicone
rubber
2. SPATIAL STRUCTURE
a. Linear:
• the structural units are connected to one
another in linear sequence.
b. Branched:
• In which side branch chains
are connected to the main ones.
c. Cross-linked polymers:
• In which the adjacent linear
chains are joined one to
another at various positions
by covalent bonds.
3. THERMAL BEHAVIOUR
a. Thermoplastic
• They are polymers which can be shaped by heat and
after cooling they maintain their shape (i.e. they soften
by heat and harden by cooling).
• In thermoplastics 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 organic solvents
• Eg : Acrylic, polycarbonate, nylon
• Linear/branched network
b. Thermoset
• They are formed into a permanent shape and set by a
chemical reaction.
• They can not be remelted and reformed into other
shape but degrade or decompose when heated to
high temperature.
• Thus thermosets can not be fused.
• The polymer chain in the thermoset polymers forms
network, with cross-links between them (primary
covalent bonds).
 POLYMERIZATION
• The process by which the monomer molecules are
linked to form a big polymer molecule
• Polymerization is a process of bonding monomer, or
“single units” together through a variety of reaction
mechanisms to form longer chains named Polymer

Polymerization

A. Addition B. Condensation
Polymerization Polymerization
A. ADDITION POLYMERIZATION
• Most dental resins are polymerized by a mech
which monomers add seq to the end of growing
chain
• Starts from active centre, adding one monomer to
rapidly growing chain.
• 2 basic types :
oOpening of carbon double bonds
oRing opening reaction
• Addition polymerization results in the formation of
large molecules without formation of by-products.
• 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),
poly(methacrylic acid) and poly (methylmethacrylate),
polyether

3 Stages

1. Initiation.
2. Propagation.
3. Termination.
1. Activation and initiation :

***Requires the presence of free radicals.

•when a free radical (R•) encounters a double bond →it
pairs with one of the electrons leaving other member of
the pair free.
•Dot = single electron

Now the monomer is a free radical

• FR generated by agents like visible light, UV light,
heat,chemical and energy transfer from another
compound.

During activation,the bond between O:O is broken,and the

electron is split .The dot adjacent the O represent unpaired
electron of free radical.
 Initiator Activator
Heat cure acrylic Benzoyl peroxide Heat
resins

Chemical activated Benzoyl peroxide Tertiary amine

resins

Light activated Camphoroquinone Visible light

resins
2. Propagation
• The middle step in chain polymerization where
successive monomers are attached to growing chain.
• In this stage, the process of electron transfer and
consequent motion of the active center down the
chain proceeds.
• The entire propagation reaction usually takes place
within a fraction of a second.
when the new free radical
formed in the initiation
stage reacts with another
monomer to add two more
carbon atoms.
This process repeats over
and over again to form
chains containing thousands
to millions carbon atoms.
3. Termination
• is nothing but stop the further propagation of chain.
• could continue until the monomers is exhausted.
• Most often the growth of a polymer chain is halted by
the termination reaction.
• Termination typically occurs in two ways:
1. Combination : the polymer's growth is stopped by
free electrons from two growing chains that join and
form a single chain
2. Disporpotionation : stops the propagation reaction
when a free radical strips a hydrogen atom from an
active chain. A carbon-carbon double bond takes
the place of the missing hydrogen.
B. CONDENSATION POLYMERIZATION
• reaction between two molecules to form a larger
molecule, with the elimination of a smaller molecule
(by-product)
• Characterized by:
1- Stepwise reaction.
2- Usually consists of more than one monomer species.
3- Small molecular weight due to by – product
elimination.
4- Slow reaction and short polymer chains.
• Examples of condensation polymerization in dentistry
are:
Polysulphides and Condensation Silicones : The low
molecular weight paste is converted to a high
molecular weight material.
• ***Water and lead sulfide are by-products of this
reaction
 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.
• Such inhibitors influences the length of the initiation
period markedly, as well as the degree of
polymerization.
• eg: hydroquinone inhibit spontaneous polymerization,
thus affect storage stability & working time of resin.
• High O2 – velocity of polymerization decreased if
polymerization occurs in open air.
 PROPERTIES OF POLYMERS
 Polymer chains are weakly bond by secondary
forces while metals have relatively strong primary
(metallic) bonds.
 The elastic moduli of polymers are much lower
than metals.
 More tendency to creep or flow.
 Sensitive to the rate of loading (or rate of
deformation).
 *At slow rate of loading they behave in a ductile
manner (more permanent deformation).
 *At high rates of loading they respond in a brittle
manner (fracture after elastic limit).
 Sensitive to temperature. They soften as they are
heated near to their glass transition temperature
(below Tg the material will be rigid).
 How to increase strength of polymer?

1.Increasing the degree of polymerization and thus

increasing M.W.
D.P.= M.W. of a polymer/ M.W. of a mer
The higher the molecular weight of the polymer →
the higher the degree of polymerization
2. Cross linking
Adjacent linear chains are joined one to another at
various positions by chemical covalent bonds.
→ 3-dimensional network cross-linked structure.
The effect of cross-linking:
A small degree of cross-linking limits the amount of
movement of the polymer chains relative to each
other when the material is stressed.
This * increases : - strength, hardness, rigidity,
resistance to action of solvents
* decreases water sorption.
Extensive cross-linking may lead to brittleness of
the material
3. Copolymers
Copolymers are polymer chains containing two or
more different types of monomeric units.
Co-polymerization processes enable chemists to
"tailor-make" molecules of predicted properties for
special applications.
Co-polymers are of three different types:
Linear co-polymer random Branched co-polymer

Graft co-polymer Block co-polymer

4. Filler
Addition of inorganic filler to the polymer forms
composite structure
Effect on the properties:
 It increases ---- strength, hardness, and
rigidity of a polymer.
 PHYSICAL STATE OF POLYMER
1. Polymer is shaped into hard and tough utility
articles by application of heat and pressure, is known
as plastics
• E.g:polysterene,PVC, PMMA.
2. When plastics are vulcanised into rubbery
products exhibiting good strength and elongation,
polymers are known as elastomers
• E.g. silicone rubber, natural rubber, synthetic rubber
3. Long filament like material whose length is atleast
100 times it’s diameter, polymers are said to be fibers
• E.g. Nylon, terylene.
 Polymers used as adhesives, potting compounds,
sealants, etc., in a liquid form are described as liquid
resins
• E.g. Epoxy adhesives and polysulphides sealants.

Other uses :
Vinyl acrylics- reliner.
Epoxy resins- die material.
Polyether- impression material.
Polysulphide
Silicone
Polycarbonates- temporary crown
Polyacrylic acid- GIC, denture base material