Prosthetic Resin Polymers

Dr Layla Abu-Naba’a
PhD, MFDRCS
Assistant Professor of Prosthodontics
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Demographic changes
Means an increased need for Prosthetic treatments

60
% population over 50

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1941 1982 2025 2050

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Prosthetic Uses

 Denture bases  Fluoride and

bleaching trays
 Denture teeth
 Facing on esthetical
 Relining Materials
crowns
 Repair of dentures  Provisional
 Provisional acrylic restorations
partial dentures  Removable tooth
 Custom impression movement devices
trays  Orthodontic retainers
 Mouth guards

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Denture base function

Distributes pressure over a wider area

So reducing bone resorption
Retains artificial teeth
Replaces missing tissue
Forms a seal for retention

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Denture Base materials

Carved ivory
Carved Wood
Vulcanite; dark, opaque (Vulcanised rubber)
Highly cross-linked Acrylic resin
Other Resin and plastic alternatives

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Plastic acrylic teeth

Bind chemically to the denture

Can be adjusted
Not cause wear of opposing tooth
Good colour match
Minor resiliency
Wear under high force occlusion
May stain with time

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Other Teeth Materials

Porcelain (high fusing ceramic)

Isosit (composite; xlinked acrylic) –

heavily xlinked

Experimental fiber-reinforced teeth

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Maxillofacial prosthesis

Needed
After trauma
Surgical defects
Birth defects

Other materials
Silicone rubber
Vinyls with
plasticizers

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Acrylic repair

Materials
Chemically cured acrylic
Light cured acrylic

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Relining Materials

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Provisional partial dentures

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Impression trays

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Record bases

Materials
Cold-curing acrylic resin
Other material
Shellac
Vacuum formed vinyl or polystyrene
Baseplate wax.

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6 Occlusal Splints
Night guards
Bleaching and fluoride
application trays

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Mouth guards

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Orthodontic applications

 Removable tooth movement devices

 Orthodontic retainers

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6 Facing of crowns
Provisional restorations
Other materials:
•Polycarbonate
•Aluminum
•Stainless steel
•celluloid

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Polymer principles

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

Poly = many
Mono = single
Mer = unit
Oligo =several
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Types and molecular weight

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

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6 Morphology
of spatial arrangements
Linear or chain polymerisation
Easily manipulated, stretched, bent,
thermoplastic, Hard
e.g. fitting surface of acrylic teeth- better
binding to denture base
Branched polymerisation
Easily manipulated, stretched, bent,
thermoplastic, More hard

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Morphology
of spatial arrangements
Cross-linked polymerisation
Strong, stiff, thermoset, wear resistant
E.g. Denture base materials, Occlusal
surfaces of actylic teeth

Coiled chains
Flexible
e.g. impression materials

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Morphology
of spatial arrangements
Crystalline polymers
Very regular arrangement in space:
strong,
stiff,
absorb less water.
Amorphous or glassy polymers
Irregular arrangement
Behaves as a brittle solid

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

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Dimensional and thermal
changes

Expansion on polymerization, exothermic

Contraction on polymerization
21vol.% If unfilled acrylic resin
6% denture resin
1-3% composites
Expansion on swelling in water
Expansion or warpage on thermal change
and reheating
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Acrylic Resin Types

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Ideal properties
Natural appearance •Low density
Easy processing •Radiopaque
Easy to clean •High thermal
Easy to repair conductivity
Inexpensive •High modulus of
Biocompatible elasticity, impact
Resistant to bacterial strength
contamination •Abrasive resistance
High strength, stiffness, •Dimensionally stable
hardness, toughness,
•Accurate reproduction
fatigue resistance
of surface detail
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 Curing methods
Chemically cured
Tertiary amine ( dimethyl-p-toluidine or sulfinic acid)
(accelerator)
Benzoyl peroxide (initiator)
Hydroquinone (inhibitor)
Heat cured
Heat and pressure control
Avoids porosity
Maximizes conversion of monomer to polymer
Light cured
Photo-initiators (camphorquinone),
Blue light,
Used for: record bases, custom tray, denture repair

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 Heat cured acrylic resin
Powder ( can have limitless life)
Beads or granules of polymethyl methacrylate
Initiator (benzoyl peroxide)
Pigments/dyes (colour vitality as cadmium, iron, organic dyes)
Optical opacifiers (tio2/zno)
Plasticizers (ethyl acrylate (internal), dibutylphthalate (external) to
make dough easier)
Synthetic fibres (nylon) Bead Polymer
Coloured fibres (blood vessels)

Liquid ( in dark bottle, avoid contamination by

powder)
Methyl methacrylate monomer
Inhibitor (hydroquinone)
Crosslinking agent
(diethylene glycol dimethacrylate, (1,4 butylene glycol dimethacrylate)

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 Chemical cured resin
Cure is initiated by a tertiarv amine (e.g. Dimethyl-p-toluidine
or sulfinic acid)

Absence of heat:
Lower molecular weight material
Lower strength properties
Higher residual monomer in the resin
Color stability is not as good- yellowing
Less contraction on cooling to room temp

Polymer beads are smaller

Faster dissolution in the monomer to produce a dough
Doughy stage is reached before the addition curing reaction – mix viscosity
is high and prevents the adaptation of the mix to the mould walls or cast -
keep readapting

Lowering of the glass transition temperature

Less build-up of internal strain
Highly susceptible to creep- distortion when in use.

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 Light activated materials
Components:
Urethane dimethacrylate matrix
Acrylic copolymer
Silica filler to control rheology
Forms
Sheets
Ropes
Curing
Light chamber- 400-500 nm
Photo-initiators (camphorquinone),
Teeth added in a second exposure over the base
Used for
Record bases
Custom tray
Denture repair
Hardness and impact strength ≈ heat cured resin
Elastic modulus < heat cured resin; deform under
mastication
Less shrinkage (3%) better fit 31

Less residual monomer

 Auto-polymerizing, pour acrylic
Reducing agent (tertiary aromatic amine or barbituric
acid derivative, NN’-dimethyl-p-toluidine) reacts with
peroxide at room temp.
Excellent detail reproduction
To be able to pour in mold, balanced size, mwt,
plasticizers and xlink agents
Reversible hydrocolloid (agar) mold can’t resist teeth
movement during pouring
Hydro pressure flask reduces air bubbles and
monomer porosities
Difficult to dewax, less monomer binding to teeth
Shortcomings:
residual monomer
↓ Cross link densities
 Creep
 Variety of products
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 High-impact acrylic
A rubber phase is added (phase inversion)
Uniformly distributed
Rubber cored polymer
Types
Butadiene + styrene = polystyrene butadiene rubber
Butadiene + MMA
PMMA + polystyrene butadiene rubber + poly(2,3-dibromopropyl
methacrylate) for opacity
PMMA = lucitone 199
Lightly xlinked or no cross linking agent is added
Rubber has a craze inhibitory effect
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 Experimental types of acrylic
All aim to increase impact strength and stiffness
Glass reinforced acrylic (failed)
Fibers may irritate patient if denture fitting surface was
abraded
Carbon fibers
Black color- used only in lingual areas
Kevler fibres (poly-p-phenylene terephthalamide)
Straw color
Poor bond between fibers and matrix
Difficult to pack
Black shadow- used only in lingual areas

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 Experimental types of acrylic
Added Bis-GMA and fiber
Flexural strength ≈ ceramics
Can be used as lingual bars and connectors
Experimental (mwt polyethylene fiber-reinforced)
Neutral color
Low density
Biocompatibility
Surface treated to enhance fabrication
Time consuming

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 Types of acrylic

Other (polystyrene,epoxy, SS)

PMMA Adhesion to
Metal- use adhesive primers
untreated porcelain teeth with organo
silane compounds

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Heat Cured Resin

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 Polymethyl methacrylate
MMA
Liquid
Heat and pressure

PMMA
(entanglements)
Powder
PMMA Particle swells Old and new
polymer chains
Powder MMA Intertwined at the
Liquid molecular level.

Activation Acrylic dough (Cohesive gel)

Initiation
Propagation
Termination
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 Setting reaction
Mixing of powder and liquid cause monomer diffusion and
softening of the surface of the powder producing the following
gelling stages:
Ratio P/L (2/1 wt%, 1.6 -1 vol%)
Sandy- initial melting of beads (not used)
Stringy or sticky- entanglements with swollen beads and
thickened interstitial monomer (not used)
Dough- gelation (used)
Rubbery- monomer penetrates to the core of beads,
plasticizing them, ↓Tg (not used)

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 Manipulation issues
P/L
Inadequate filling by monomer
Weak material properties
Porosity
↓P/L
Excessive polymerisation shrinkage
Poor fit
Light color as powder holds the pigments

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 Manipulation issues
Curing before monomer diffuse to bead ( before dough
stage)
↓ flexural strength
cracks between linear polymerised interstitial gel and cross linked beads
More shrinkage contraction by the loss of pressure produced by the dough
to compensate for it
Curing in dough stage
monomer penetrate the beads
dissolves beads allows cross-linking agent to penetrate
interpenetrating polymer network IPN.
Packing in the rubber stage
Less extrusion of excess acrylic from flask
Extra pressure in the mould
Fracture the cast
less flow around teeth
Dislodgment of teeth into mould

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Manipulation issues
Control of color
Pigments position
Inside beads
surface of beads
– polymer should be added to the monomer slowly so it will not
washed off by too rapidly
Blood vessel resembling Fibers aggregate in the bottom
of bottle
– Shake powder well before use
Mould Lining
resin may penetrate rough plaster and adhere
a separating medium must be employed
solution of sodium alginate
tin foil.

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Manipulation issues
Control of Processing strains
Shrinkage in restricted mould cause internal strain
On release of stress (flask opening) it may give
Crazing
Warpage
Distortion
These are reduced by the slightly extra packed material
that flow into shrinkage spaces when temperature is
higher than Tg (heated flask)
Manipulation further reduces strains by
Using acrylic teeth
Cooling the flask slowly

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Flasking steps

Flasking
Dewaxing
Putting a separating medium
Placing acrylic dough
Packing
Heat curing

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 Flasking
Wax-up

Melt out the wax

Packing

Curing

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Flasking for heat cured resin
Flasking options with acrylic dough:
Trial-packing, trimming, repacking
Packing-only
Poured resin (e.G., Lucitone fas-por)
Injection moulding

Heat and pressure control

Aim to produce radicals and initiate polymerization
Reaction is thermally activated and generates heat as
well
Reaction conversion is about 98 to 99.5%
MMA: tbp = 100c (p= 1 atm); 140c (p= 2 atm)

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 Heat curing cycles
Fast cycle
Cure at 71-72°C for 30-90 min
100°C for 30 min.
Slow cycle = cure at 71-72°c for 10 hrs
[A slow cycle is better with larger amounts of
material.]
[Generally, slow cures result in better
dimensional accuracy.]
Other cycles are done as recommended
by manufacturers

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Heat curing cycles

Rapid heating:
Excess radical release
Extra xlinking and branching of interstitial
polymer
More residual monomer
Reduced toughness
Heat builds up from exothermic rxn
Porosity
Loss of strength
Bad esthetics (opaque and cloudy color)
Possible fouling

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Heat curing cycles

Slow :
Sufficient radical release
Adequate xlinking and branching between high
mwt polymer chains
Increased toughness
Sufficient radical ends increase monomer
incorporation in growing chains
Xlinking agents polymerized, reducing their
plasticizing effect (in their non bound state) and
reduce creep
Produce an annealing effect easing stresses
produced from shrinkage, reducing crazing and
distortion
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Heat curing cycles

Pressure control
Places compressive force
Compensates for polymerization shrinkage
Increase flow of dough around teeth, more
monomer wetting and surface dissolution,
stronger bond
Oozes out excess dough
Some hybrid systems begin polymerization
from one side to allow dough to cover for
shrinkage

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Heat curing cycles

Microwave curing
Uses a microwave
Flasks are non metalic
Reduced time

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Denture shortcomings

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 Denture Radiolucency
Problems when accidents displace fractured
segments
Lungs
Skull
stomach
Salts and fillers reduce esthetics, strength
Organo-metalics are toxic
Bromine containing organics lack heat stability, must be
added in quantities that plasticize the denture, causing creep
and water sorption
Phase separating bromo-polymer in beads reduce the
previous effects
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 Mechanical properties
Failure to Moderate strengths:
impact resistant denture is low
Low elastic and flexural modulus
lack of fracture toughness
30% of denture repairs involve midline fractures
which are most prevalent among upper dentures.
dropped denture does not necessarily break instantly
a crack continue to grow and failure due to flexural fatigue.
Failure due to poor quality processing
Lack of bonding between the resin and the acrylic teeth and
weak interface
Crazes due to processing faults or exposure to solvents is
another possibility.
Creep
Reduced by cross linking
Heat cured < cold cured

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 Internal denture porosity
Inherent porosity: Minimized by
Not seen by vision Use heat cured resin
1-2% of residual Pack denture under
monomer correct pressure
Leaks Use correct P/L
Replaced by fluids Use the glaze after
polishing

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 Internal denture porosity

Irregular porosity: Minimized by

Seen by vision Use correct P/L
Add liquid first
Not regular on
Mix well
denture surface
Cover the mix before
P/L heterogeneity dough stage
Air incorporation Can use the vibrator
(spherical
pores)

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 External denture porosity
Irregular surface Minimized by
deficiencies: Mold dough by hand
Seen by vision into small areas
Insufficient pressure Place sufficient
Dough was not molded material in flask
correctly by hand leaving Pack under correct
surface blisters and pores pressure
Insufficient dough

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 External denture porosity
Irregular porosity: Minimized to by
Shrinkage by Pack under pressure
polymerisation (5-8% vol Slight extra denture
or 0.2 -0.5% linear) material can overcome
Further shrinkage by shrinkage and
cooling to room maintain pressure
temperature (single packing)
Can compensated for by Pack in dough stage
the post dam technique

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 Internal denture porosity
Minimized by
Gaseous porosity Avoid high processing
Seen by vision temperatures
Avoid extra monomer
Volatisation of than recommended for
monomer by P/L
Localized MMA boiling Raise heat slowly and
Common in thicker evenly around the
portions flask

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 Gaseous porosity

Avoid high processing temperatures

160
140
Temperature 0C

120
100

Incorrect 80
cycle 60
40
20 Correct
cycles
0

Time (min) 60
Crazing

Area of localised region of high plastic

deformation which may fill by voids
Crazed region can still support stress
As the voids in the crazed region grow, they become
separated only by thin fibrils of polymer
Fibrils fail and a crack is formed
Crack will grow under an externally applied load
Cause denture failure by brittle fracture.
Caused by
Internal strains in flask
Heat (due to polishing)
Differential contraction around porcelain teeth
Attack by solvents such as alcohol

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Crazing

Avoid internal strain during polymerisation

Slow cooling of the flask
Use single trial packing
Use cross linked polymer types
Avoid extra stress during function
Use acrylic rather than porcelain teeth
Do not overheat on polishing
Keep denture away from solvents
Avoid denture drying
Polish after each adjustment
Use glazes for surface

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 Dimensional changes on
processing
Expansion on heating flask; heat evenly
Expansion on polymerization, exothermic
Contraction on polymerization (21vol.%);
Contraction on cooling to room temperature;
Expansion on swelling in water;
Expansion on thermal change to 32c.

Net result– should be near zero

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Warpage on drying

Contraction on evaporation of
absorbed water
Don’t leave denture outside the mouth
dry

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 Adverse reactions to PMMA
Most common in dental
laboratories
Associated with regular
contact with monomer
when handling the dough
Irritant contact Must avoid direct contact
dermatitis Rubber gloves may not
provide sufficient
protection
Barrier creams can help

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 Adverse reactions to PMMA
Must ensure full cure of denture
Allergic contact dermatitis
Usually associated with Avoid relining procedures
release of May use an extra cycle of
residual monomer
Benzoic acid polymerisation – but denture
Types
Immediate
may warp
Delayed hypersensitivity May need to consider
(type IV)
Heat cured resin < chemical alternative material such as
cured polycarbonate if Delayed
hypersensitivity

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 Adverse reactions to PMMA

Further reading:
Hensten-petterson & jacobsen. J prosthet dent
1991; 65: 138
Kaber. Int dent J 1990; 40: 359
Http://www.Shef.Ac.Uk/uni/project/arrp/

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 Thermal properties
Low Thermal conductivity

during denture processing heat cannot escape – prone to

gaseous porosity
isolates from any sensation of temperature – throat burns

High Coefficient of Thermal Expansion

Porcelain teeth may be lost due the differential

expansion and action
Warpage if denture is cleaned with hot water

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 Water Sorption
PMMA will absorb water by polar nature (1.0-2.0% wt)
May compensate for processing shrinkage
Weeks of continuous immersion in water to reach a
stable weight

Solubility
Solvents (e.G. Chloroform, alcohol)
Xlinked are insoluble in most of fluid intakes
Weight loss will occur, due to leaching of the
Monomer
Pigments and dyes.

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 Ideal properties achieved?
Natural appearance 
Easy processing 
Easy to clean 
Easy to repair 
Inexpensive 
Biocompatible 
Resistant to bacterial contamination x
High strength, stiffness, hardness, toughness X
Low density 
Radiopaque X
High thermal conductivity X
Dimensionally stable
X 70

Accurate reproduction of surface detail 

 More

DB bonding to alloy framework

Acrylic-metal leakage

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Other Denture Base materials

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 Injection molded plastic
Types
Polycarbonates
Nylon
Advantage:
Consistent mwt
Substitute acrylics in sensitive patients
Disadvantage
Must use dry mold, slow heating and cooling
Under filled molds by inadequate spruing or underheating
Low melt temp cause high injection forces, moving teeth in mold
Cost of equipment
Difficult to attach to teeth
Small market segment
Can explode if high heat and wet molds
Overheating cause depolymerization, oxidation, porosties
Loss of strength
Bad esthetics (opaque and cloudy color)
Possible fouling

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Polycarbonates

Tough plastic
Injected in dry molds
A high melt viscosity
Problems in binding to teeth

May de-polymerize explosively in the

presence of heat and water
No cross linking –
Poor solvent resistance
Poor craze resistance

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Nylons and polyamides

Polyamide = diacid + diamine

Conventional nylon failed
Excessive water sorption
Poor creep resistance
Biodegradation

Glass (beads or fibers) reinforced nylon

Less water sorption
Fibers better in stiffness(≈ acrylic) than beads
Fibers may irritate patient if denture fitting surface was abraded

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Cellulose product

Camphor used as plasticiser

Warpage in mouth
Camphor leached out
Loss of color
Taste
Blistering
Staining

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Phenol Formaldehyde (Bakelite)

Difficult to process
Lost its color with function

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Vinyl resins

Low resistance to fracture

Fatigue failure

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Relining Materials

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 Denture base reprocessing:

Hard and soft tissue changes every 5-8 years

Require modifying denture base:
Relining  resurfacing of the tissue surface
Rebasing  replacement of entire denture
base

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 Soft denture lining material

Uses:
After surgery
Immediate dentures
Sores
Undercuts which are not removed by surgery
Ill fitting denture

can be done
In lab
Chair side

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Ideal lining material properties
Durability: but hardens in short time
(1-4w, 1-3 y)
Dimensional stability
Resistance to fouling
Water absorption
Osmotic presence of soluble material
Resistance of Biodegradation
Could it bond old acrylic
Inhibit candida growth
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 Lining materials–acrylic based
Glassy MMA + high conc. of plasticizers
Plasticizers:
Free: diffuse out reducing the resiliency
Bound in cured matrix – failed clinically
Has lower rate of polymerization
Phase separation
Water accumulate in plasticizer rich phase
Soluble impurities cause more osmotic pressure
Swells and distorts
Discoloration
Bad taste
Exothermic rxn
Bad taste 83
 Lining materials–acrylic based
Soft acrylics that have ↓Tg
EMA (ethylmethacrylates)
Beads coploymer
Ethyl methacrylate + isobutyl methacrylate
Ethyl methacrylate + ethoxyethyl methacrylate
– Have unpleasant odour
Monomer
MMA Tg > room temp Less irritant to patients
Isobutyl methacrylate Tg < room temp (polished after placing
in iced water), Dimensional instability
Plasticizer in monomer trapped in beads (25-50%)
Phthalate ester – leach out by time
Avoid heat, strong bleaching agents that reduce resilience
84
 Lining materials–acrylic based
Soft acrylics that have ↓Tg
Hydroxy EMA
Water is the plasticizer
Swelling of liner may make it distort
Ions enter and may crystallize inside matrices thus
hardening the liner

Polymerisable plasticisers
Beads ploymer
Ethyl methacrylate + isobutyl methacrylate or
Monomer
Alkyl maleate or
Alkyl itaconate + Tridecyl methacrylate +
2-diethylhexyl maleate, ethylene glycol dimethacrylate
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 Tissue conditioners
Differ from soft lining material by the following
Different viscoelastic properties
Flowable on insertion responding to
– Masticatory forces
– Lingual forces
– Border moulding forces
Increase viscosity on setting
Flows slowly responding to persistent heavy masticatory forces
after setting
– Useful to fill space after tissue swellings resolve
– Can be used as a functional impression
Reaction
Gel formation not polymerization
Alcohol swells beads and ↓ their Tg
Beads become tacky by entanglements and  cohesive strength
86
 Tissue conditioners
Differ from soft lining material by the following
Composition
• Old- plasticine
• Old- chewing gum
• Ethyl methacrylate copolymers
• Or small mwt polymers

Plasticisers:
ethyl alcohol or
aromatic esters (butylphthalyl butylglycolate)
hemical cleaning damages the liner
– Use plain soap and water

87
 Tissue conditioners
Differ from soft lining material by the following
Alcohol problems:
Leak and replaced by water- so harden days up to 14 days
High conc. Can give a sting sensation
Can give a false positive on breathalyser test
Reduce leach of plasticisers by glazing or semiset MMA
Very susceptible to infection
– Incorporate antimicrobials as
» silver zeolite
» itraconazole

Chemical cleaning damages the liner

– Use plain soap and water
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Silicon - RTV
Room temperature vulcanizing silicones (RTV)
Polymethyl siloxane polymer
It sets by crosslinking of existing polymers
Heat
Tetraethyl silicate
Condensation minimal xlinking
Poor tear resistance
Poor abrasion resistance
Poor adhesion to denture
Use adhesive or coupling agent
Osmotic pressure effects
Buckling and swelling with water
Poor resistance to cleansers
Biocompatible
Dimensional stability
May foul by Candida
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Silicon – Heat cured
More xlinking
Poor tear resistance
Adequate adhesion to denture
Can use siloxane methacrylate as a binder to heat
cured additional silicon
Resistant to aqueous environment and Osmotic
pressure effects
better resistance to cleansers
Poor tear resistance
Poor abrasion resistance
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Other acrylic products

91
 Denture base hygiene
1. Clean with toothbrush and warm soap-and-water
2. Use low abrasive cleaners

2. Avoid oxidizing or Cl-containing materials

• Bleaching the color
• Reduces strengths of denture
• Reduces fatigue resistance
3. Diligently clean both the top and tissue-borne surfaces
4. Clean with benzalkonioum

92
Thank you

93
References

Philips Science of Dental Materials

Dental Materials and Their Selection
Applied Dental Materials
Dental Materials. Clinical Applications for Dental
Assistants and Dental
Introduction to Dental Materials
RPD acrylic materials by Dr Stephen C. Bayne
Dr Layla Abu- Naba’a

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