SYNTHETIC RESINS IN PROSTHODONTICS

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Introduction

 Resin - a broad term used to describe natural or synthetic

substances that form plastic materials after polymerization.

 Resin - solid or semi-solid amorphous natural organic substances

that are transparent or translucent.

 Resin - usually formed in plant secretions and are soluble in

organic solvents but not water.

Classification

1) Depending on THERMAL BEHAVIOUR:

Thermoplastic: Resins, which soften again when reheated.

Thermosetting: Resins, which are resistant to change after further

application of heat.

2) Depending on particular FORM and MORPHOLOGY of the

MOLECULE:

Fiber resin

Hard and rigid resin

Rubber like resin

3) Depending on enormous IMPACT on dentistry:

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Sealants

Bonding materials

Restorative materials

Veneering materials

Dentures

Impression materials

Dental resins

The dentist uses a thermoplastic resin to restore and replace missing

teeth and tooth structure.

If all teeth are missing, a denture base resin is used to make an

artificial denture.

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Requisites for dental resin

1) Should exhibit a translucence or transparency such that it can be

made to duplicate esthetically the oral tissues it is to replace.

2) Should be no change in colour or appearance of the material

after its fabrication.

3) Should not expand, contract or warp during processing or during

use by the dentist.

4) Should posses adequate strength, resilience and abration

resistance.

5) Should be impermeable to oral fluids.

6) Should chemically bond to the tooth, if it is used as filling

material or cement.

7) Should be tasteless, odourless, non-toxic and non-irritating to

the oral tissues.

8) Should have a low specific gravity.

9) Softening temperature should be well above the temperature of

any hot foods or liquids taken into the mouth.

10) Should be possible to repair the resin easily and efficiently, in

case of breakage.

11) Fabrication of the resin into a dental appliance should be easily

done.

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 12) Should not produce toxic fumes or dust during handling and

manipulation.

Polymerization

It is defined as a series of chemical reactions by which the

macromolecule (polymer) is formed from large numbers of molecules

(monomer).

Types of polymerization mechanisms

a) Condensation polymerization.

b) Addition polymerization.

a) Condensation polymerization

Also known as step-growth polymerization.

The primary compounds react, with the formation of byproducts such

as water, halogen acids, and ammonia.

The structure of the monomers is such that the process can repeat itself

and build macromolecules.

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Steps in condensation polymerization

Formation of a dimer.

Then longer chains, including trimers and tetramers are formed through

esterification reactions.

Reaction showing condensation polymerization where water is formed

as by-product.

Process of condensation polymerization

1) Polymerization is accompanied by repeated elimination of

small molecules.

2) Functional groups are repeated in the polymer chain.

Materials which use condensation polymerization are

Polysulfide.

Condensation silicone.

b) Addition polymerization

Most resins are polymerized by this addition polymerization.

There is no change in composition during addition polymerization.

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The macromolecules are formed from smaller units, without change in

composition.

It can readily produce giant molecules of almost unlimited size.

Addition polymerizable compound should have an unsaturated group.

Stages in addition polymerization

It occurs in four stages:

1) Induction.

2) Propagation.

3) Termination.

4) Chain transfer.

1) Induction

Induction period is the time during which molecules of the initiator

become energized or activated.

To start the process, free radicals must be present.

Free radicals can be generated by activation of monomer molecules.

These free radicals are called initiators.

 Most common initiator is benzoyl peroxide.

 Free radicals are obtained by heating benzoyl peroxide.

 It decomposes and releases two free radicals per molecule.

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  This initiates the polymerization of methyl methacrylate

monomer.

 This activation occurs rapidly at 50* to 100*c(heat

activation).

 The higher the temperature, shorter the length of the

induction period.

 Chemical activation is at oral temperature.

 It has two reactants that generate free radicals.

 The two reactants are tertiary amine (activator) and benzyl

peroxide (initiator).

 This is used in self-cure resins.

 The third induction system is light activated.

Here photons activate the initiator to release free radicals.

To trigger this reaction, light with a wavelength of about 470nm is

used.

2) Propagation

As little energy is required once the growth has started, the process

continues with considerable velocity.

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The reaction should continue until all the monomer has converted to a

polymer.

3) Termination

Chain reactions can be terminated either by direct coupling or by the

exchange of a hydrogen atom from one growing chain to another.

4) Chain transfer

Chain termination can occur from chain transfer.

Chain transfer is the transfer from an activated radical to an inactive

molecule and a new nucleus is created for further growth.

Copolymerization

The process of formation of a polymer from two or more chemically

different monomers is called co polymerization.

The polymer so formed is called copolymer.

In a copolymer, the number and position of the different type units may

vary among the individual macromolecules.

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Copolymer structure is idealized because the occurrence of alternately

placed radicals in the chain would not occur.

The composition of the copolymer depends on the relative reactivities

of the different molecules and the molecules of same composition.

Types of copolymers are

Random copolymer.

Block copolymer.

Graft copolymer.

In a random copolymer, the different monomer units are randomly

distributed along a chain.

In block copolymer, the identical monomer units occur in relatively

long sequences along main polymer chain.

In graft copolymers, sequences of one of the monomers are grafted

onto a “backbone” of the second monomer species.

Cross linking

Cross linking is defined as joining or bridging through certain reactive

side chains, to form molecular networks.

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It provides a sufficient number of bridges between the linear

macromolecules to form a three-dimensional network.

This network alters the strength, solubility, and water sorption of the

resin.

Plasticizers

They are added to resins to reduce their softening or fusion

temperatures.

It acts to partially neutralize secondary bonds or inter molecular forces

that prevent the resin molecules from slipping past one another when

the material is stressed.

Commonly used plasticizer is butyl methacrylate.

Plasticizers reduce the strength, hardness, and the softening point of

the resin.

Types of resins

Acrylic resins:

The acrylic resins are derivatives of ethylene and contain a vinyl group

in their structural formula.

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 H2C=CH

There are two acrylic resins that are of dental interest:

Series derived from acrylic acid.

CH2=CHCOOH

Series derived from methacrylic acid.

CH2=C (CH3) COOH

2) Methyl methacrylate:

It is not used directly in dentistry in moulding procedures.

It is a clear, transparent liquid at room temperature.

Composition

It is used as liquid monomer and powder polymer.

3) Poly methyl methacrylate:

It is a transparent resin of remarkable clarity.

It is a hard resin and is extremely stable.

It softens at 125*c and it can be moulded as a thermoplastic material.

It absorbs water by a process of inhibition.

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4) Multi-functional methacrylate:

Bowen’s resin or Bis-GMA is used in dentistry.

It is an aromatic ester of dimethacrylate, synthesized from an epoxy

resin and methyl methacrylate.

Pure Bis-GMA is extremely viscous.

Urethane dimethacrylate,

Dipentoerythiol penta-acrylate monophosphate,

Polyacrylic acid

Are recently introduced multi-functional methacrylates.

Denture base resins

Most denture base resins are fabricated using common polymers.

Such polymers are chosen based on their availability, dimensional

stability, handling characteristics, colour and compatibility with oral

tissues

Types of denture base resins commonly used in dentistry are:

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1) Heat activated denture base resins.

2) Chemically activated denture base resins.

3) Light activated denture base resins.

4) Miscellaneous resins.

Heat activated denture base resins

Composition

Contains powder and liquid components.

Powder

consists of

Pre-polymerized spheres of poly methyl methacrylate.

Small amount of benzoyl peroxide which acts as an initiator.

Liquid :

consists of

Un polymerized methyl methacrylate.

Small amounts of hydroquinone which acts as initiator.

Glycol dimethacrylate, which acts as, cross-linking agent.

Techniques involved in manipulating heat activated denture base resins

are:

Compression moulding technique.

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Injection moulding technique.

Compression moulding technique

Steps involved in mold preparation:

a) Complete tooth arrangement prepared for flasking process.

b) Master cast embedded in properly contoured dental stone.

c) Fully flasked complete denture after pouring dental stone.

d) Separation of flask segments during wax elimination process.

e) Application of alginate based separating medium.

Steps involved in resin packing:

f) The polymer and monomer are mixed in proper proportions.

Accepted polymer: monomer ratio is 3:1 by volume.

g) Properly mixed resin is placed into the mold cavity.

h) Flask assembly is placed into a flask press and pressure is applied.

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i) Excess material is carefully removed from the flask.

j) The flask is transferred to a flask carrier that maintains pressure

during processing.

Polymer- monomer interaction

When they are mixed, a workable mass is produced and passes through

five stages.

They are:

Sandy stage.

Stringy stage.

Dough like stage.

Rubbery stage.

Stiff stage.

Sandy stage

Little or no interaction occurs.

Polymer beads remain unaltered.

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Consistency of the mixture can be described as “coarse” or “grainy”.

Stringy stage

Monomer attacks the surfaces of individual polymer beads.

Some polymer chains are dispersed in the liquid monomer.

These polymer chains uncoil, there by increasing the viscosity of the

mix.

Stringiness” or “stickiness” characterizes this stage when the material

is touched or drawn apart.

Dough like stage

An increased number of polymer chains enter solution.

Hence a sea of monomer and dissolved polymer is formed.

A large quantity of undissolved also remains.

The mass behaves as pliable dough.

It no longer adheres to the surfaces of the mixing vessel or spatula.

The material should be packed during the latter phases of the dough

like stage.

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Rubbery stage

Monomer is dissipated by evaporation and by further penetration into

remaining polymer beads.

The mass rebounds when compressed or stretched.

Stiff stage

This occurs on standing for a long period.

This is attributed to the evaporation of monomer.

The mixture appears very dry and is resistant to mechanical

deformation.

Packing

Introduction of denture base resin into the mold cavity is termed as

packing.

The packing process should be done while the denture base resin is in

dough like stage.

Steps in packing

Resin is placed into the flask that houses the prosthetic teeth.

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A polyethylene sheet is placed over the resin.

The flask is reassembled and is placed into a press, and pressure is

applied. (Trial closure)

The flask is again separated and the sheet is removed.

Excess resin (flash) is removed.

A fresh polyethylene sheet is placed and the flask is re-closed and

again is placed into the press.

Another trial closure is done.

Trial closures are repeated until no flash is observed.

Then definitive closure of the mould is accomplished.

During final closure no polyethylene sheet is placed.

The flask is then transferred to a flask carrier and pressure is

maintained.

Then processing of the denture base is done.

Injection moulding technique

• A specially designed flask is used in this method.

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Steps involved in this metho:

Complete tooth arrangement prepared for flasking process.

b) Master cast is embedded in properly contoured dental stone.

c) Placement of sprues for introduction of resin.

d) Fully flasked complete denture after pouring dental stone.

e) Separation and placement of the flask into a carrier that maintains

pressure after wax elimination.

f) Injection of resin and placement of assembly into water bath for

processing.

Polymerization cycle

The heating process used to control polymerization is termed as

polymerization cycle or curing cycle.

Commonly used cycle is

Processing the resin at 74*c for 2hrs and then increasing the

temperature to 100*c and processing for 1hr.

• After completion of polymerization, the denture flask should

be cooled slowly to room temperature.

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Chemically activated denture base resins

 These resins are also called as cold curing, self-curing or auto

polymerizing resins.

 This is because they don’t need thermal energy for polymerization.

 Chemical activators like dimethyl-para-toludine is used in the

monomer to induce polymerization.

 Techniques involved in manipulating chemically activated denture

base resins are:

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 Compression moulding technique.

Fluid resin technique.

Compression moulding technique

a) The mould preparation and resin packing are the same as that of heat

activated denture base resins.

b) After final closure, pressure must be maintained throughout

polymerization process.

c) Initial hardening takes place within 30min of final flask closure.

d) The flask should be held under pressure for minimum of 3hrs to

ensure sufficient polymerization.

Fluid resin technique

• This technique has a pourable, chemically activated resin.

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Steps involved in fluid resin technique:

a) Completed tooth arrangement is positioned in a fluid resin flask.

b) Flask is filled with a reversible hydrocollid investment medium.

c) The tooth arrangement is removed from the investment.

d) Sprues and vents are prepared from introduction of resin.

e) The prosthetic teeth are repositioned.

f) The resin is poured into the flask.

g) After polymerization, the completed denture is recovered.

Advantages

• Improved adaptation to underlying soft tissues.

• Decreased probability of damage to teeth and denture during

deflasking.

• Reduced material costs.

• Simplification of flasking, deflasking and finishing procedures.

Disadvantages

• Shifting of teeth during processing.

• Air entrapment within denture base.

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• Poor bonding between denture base and teeth.

Light activated denture base resins

• These resins use visible light for their polymerization.

• This is a single-component denture base resin.

• It’s supplied in sheet and rope forms and is packed in light-proof

pouches to prevent inadvertent polymerization.

Composition

• Urethane dimthacrylate.

• Microfine silica.

• Acrylic resin - organic filler.

• Visible light - activator.

• Camphoroquinone - initiator.

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Steps involved in manipulating light activated denture base resin

are

a) Teeth are arranged and the denture base is molded on an accurate

cast.

b) Denture base is exposed to a high intensity visible light source for

an appropriate period.

c) After polymerization, the denture is removed from the cast, finished

and polished.

Miscellaneous resins

1) Repair resins:

• Fractures of denture may be repaired using compatible resins.

• Repair resins may be light activated, heat activated or chemically

activated.

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Steps involved in repair

a) Fractured components of prosthesis are realigned.

b) They are luted with adherent wax or modeling plastic.

c) Then a repair cast is generated using dental stone.

d) Fracture surfaces are trimmed to provide sufficient room for repair

material.

e) The cast is coated with separating medium.

f) The denture base sections are repositioned and affixed to the cast.

g) Chemically activated resin is prepared as repair resin.

h) A small amount of monomer is painted onto prepared surfaces of the

denture base to facilitate bonding of repair material.

i) Monomer and polymer are added in increments.

j) Then the assembly is placed in a pressure chamber for

polymerization.

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2) Relining resin denture bases

• Relining is defined as the replacement of tissue surface of an

existing denture.

Steps involved

a) First impression of soft tissues is obtained using the existing denture

as impression tray.

b) A stone cast is generated.

c) The assembly is invested in a denture flask.

d) The impression material is removed from denture.

e) A chemically activated resin is chosen and is introduced and shaped

using compression moulding technique.

f) Then it is compressed and permitted to polymerize.

3) Rebasing resin denture bases

• Rebasing is defined as the replacement of entire denture base.

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Steps involved

a) Impression is obtained using existing denture as custom tray.

b) Stone cast is fabricated.

c) The cast and denture are mounted in a reline jig, to maintain the

correct vertical and horizontal relationships between cast and surfaces

of teeth.

d) Indices for occlusal surfaces of teeth are established.

e) The denture is removed and teeth are separated.

f) The teeth are repositioned in their indices and are waxed to new base

plate.

g) The completed tooth arrangement is resealed to the cast and the

assembly is invested.

h) After removal of wax and baseplate, resin is introduced and then

processed.

4) Short term and long term soft liners

• Soft liners serve as “shock absorber” and absorb the energy produced

by masticatory impact.

• Commonly used liners are plastcized acrylic resins.

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• These resins may be heat activated or chemically activated.

• Chemically activated soft-liners are called short term soft-liners.

• Heat activated soft-liners are called long term soft liners.

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Composition

Chemically activated soft liners

Powder:

Poly methyl methacrylate or Poly ethyl methacrylate.

Liquid:

60% to 80% dibutyl phthalate(plasticizer).

Heat activated soft liners

Powder:

Polymers and co-polymers of acrylic resin.

Liquid:

Acrylic monomers and plasticizers.

Steps involved in manipulation

a) Relief is provided to permit acceptable thickness of the material.

b) Adhesive is applied to the surface of denture.

c) The material is mixed, applied to the denture.

d) Compression moulding is done.

e) It is permitted to polymerize.

5) Resin impression tray and tray materials

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• They are used in impression procedures.

• They are fabricated to fit specific arches.

• They are also called as custom trays.

Steps involved

a) Preliminary impression is made using stock tray.

b) Cast is generated.

c) Spacer is placed and separating medium is applied.

d) Resin dough is formed, rolled into a sheet, adapted to the cast.

e) Then it is allowed to polymerize.

• Material of choice is chemically activated resin

6) Denture cleansers

• These are used for cleaning dentures.

• Commercial cleansers are in powder and tablet form.

Composition

• Alkaline compounds, detergents, sodium perborate and flavoring

agents.

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Resin teeth

• More than 60% of artificial teeth are made of acrylic and vinyl

acrylic teeth.

• Most resin teeth are based on poly methyl methacrylate chemistries.

• Poly methyl methacrylate resin in prosthetic teeth is as that used in

denture base resins.

• Chemical bonding to prosthetic teeth and heat activated denture base

resins is extremely effective.

• Bonding between prosthetic teeth and chemically activated resins is

through mechanical retention.

• Prosthetic teeth can also be fabricated using porcelain.

Advantages of resin teeth over porcelain teeth

1) Greater fracture toughness.

2) Easier to adjust.

3) Greater resistance to thermal shock.

4) Chemical bonding with denture base resins.

Materials in M.F.P

• Maxillo facial prosthesis is used to mask maxillo facial defects.

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Requisites of ideal material

• Inexpensive

• Biocompatible

• Strong

• Stable

• Skin like colour and texture.

Materials

1) Latexes are soft, inexpensive materials used to create life like

prostheses.

Disadvantages

• Weak, rapid degeneration, color instability, allergic reactions.

• Recently developed latex: tripolymer of butyl acrylate, methyl

methacrylate and methyl methacrylamide.

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2) Vinyl Plastisols are thick liquids with small vinyl particles

dispersed in a plasticizer. Colorants are added to match individual skin

tones.

Disadvantages

• Harden with age.

• Ultra violet light also has adverse affect.

3) Silicone rubbers are of two types:

a) Heat vulcanizing silicones.

b) Room temperature-vulcanizing silicones.

Room temperature vulcanizing silicones

• Supplied in single-paste systems.

• These are coloured using dyed rayon fibers, dry earth pigments, and

oil paints.

Heat vulcanizing silicones

• Supplied as a semi-solid or putty like material.

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• It requires milling, packing under pressure, and a 30-minute heat

application cycle at 180ºc

Disadvantage

• Requires milling machine and a press.

4) Poly urethane polymers are most recently used materials. It is

allowed to polymerize at room temperature.

Disadvantage

• Rapid deterioration.

Restorative resins

• Synthetic resins evolved as restorative materials because they are

insoluble, aesthetic, insensitive to dehydration, inexpensive and

easily to manipulate.

Composite restorative materials

• Composite material is a compound of two or more different materials

with properties that are superior or intermediate to those of the

individual constituents.

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• Composite materials contain a number of components.

• The following are the components of composite resins:

1) Resin matrix

• Composite materials use monomers that are aromatic or aliphatic

diacrylates. Bis-GMA, urethane dimethacrylate, and triethylene

glycol dimethacrylate are commonly used dimethacrylates.

2) Filler particles

• Filler particles improve the properties of the matrix if they are well

bonded to the matrix.

• Grinding or milling quartz or silica whose particle size ranges from

0.1 to 100um commonly produces them.

Advantages of filler particles

• Polymerization shrinkage is reduced.

• Water sorption is less.

• Thermal expansion is less.

• Compressive and tensile strength are increased.

• Modulus of elasticity is improved.

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• Abration resistance is also increased.

3) Coupling agents

• A coupling agent provides the bond between the two phases of the

composite.

• Titanates and zirconates are used as coupling agents.

• Also organosilanes such as alfa methacryloxypropyltrimethoxy

silane are most commonly used.

4) Inhibitors

To minimize or prevent spontaneous polymerization of monomers,

inhibitors are added to the resin.

• A typical inhibitor is butylated hydroxytoluene in concentration of

0.01wt%.

5) Optical modifiers

• These are added to have visual coloration.

• Titanium dioxide and aluminium oxide are commonly used.

Classification of composite resins

• This is based on particle size:

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 1) Traditional composite - 8 to 12um.

2) Small particle-filled composite - 1 to 5um.

3) Microfilled composite - 0.04 to 0.4um.

4) Hybrid composite - 0.6 to 1um.

Prosthodontic resins

Veneering resins

• Initially heat-polymerized poly methyl methacrylate was used.

• Then it was improved by the addition of fillers and cross-linking

agents.

• Recently used resins are bis-GMA, urethane dimethacrylate, and 4,8-

dimethacryloxy methylene-tricyclo-decane.

Bonding with metal substrates

• First the resins were bonded mechanically using wire loops or

retention beads.

• Now micro mechanical retention is created by acid-etching the base

metal alloy.

• The chemical bonding systems used are:

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 1) 4-META.

2) Phosphorylated methacrylate.

3) Epoxy resin.

4) Silicon dioxide.

• These systems are flame sprayed to the metal surface followed by

the application of silane coupling agent.

Advantages of veneer resins over ceramics

• Ease of fabrication.

• Intraoral reparability.

• Less wear of opposing teeth or restorations.

Disadvantages

• Low proportional limit.

• Distortion on occlusal loading due to pronounced plastic

deformation.

• Surface staining and intrinsic discoloration.

• Wear during tooth brushing.

• Dimensional change during thermal cycling and water sorption.

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Uses of veneering resins

• For resin bonded metal crowns.

• For masking tooth discoloration and malformation.

• As preformed laminate veneers.

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