SYNTHETIC POLYMERS

DENTURE BASE POLYMERS

DENTURE LINING POLYMERS
TEMPORARY CROWN AND BRIDGE MATERIALS
SURFACE MODIFICATION
ALLERGY

Krisztina Ungvári
University of Szeged, Faculty of Dentistry
Department of Prosthodontics
05.10.2019



 Parts Applied Dental
Materials

Synthetic polymers Chapter 12

Denture base polymers Chapter 13
Denture lining polymers Chapter 14
Temporary crown and bridge Chapter 26
materials

Gypsum Dental cements

products
Porcelain crowns

Inorganic Ceramics
salts

Impression
materials
Elastomers Metals,
Components
Polymer alloys of dentures
composites

Polimers
Wires
Direct filling
materials
Cast
Denture restorations
bases
Direct filling
materials
 Synthetic polymers
❖ high molecular weight
❖ chain-like molecules
❖ monomers are converted to polymers:
polymerisation
❖ Monomers: are liquids or gases
❖ Polymers: are crystalline or amorphous
solids
❖ consistency from rigid to soft and rubbery

 Polymerisation
Addition Condensation
❖ A+B=C ❖ A+B=C+d

❖ “A”: reactive species ❖ “A”: organic acid

❖ “B”: monomer ❖ “B”: alcohol
❖ “C”: larger reactive species ❖ “C”: esther
❖ “d”: bioproduct (water)



 addition

ionic (nature)
Free radicals
initiator (relatively weak bond, benzoyl peroxide)

❖ with heating

❖ with chemical activator (low temperature)

radiation sensitive initiator (benzoin methyl ether

due to ultraviolet radiation, or ketones)

initiator

activator
 monomers in addition
❖ alkene typ
❖ C=C

 polymerisation process
❖ activation:
decomposition of initiator (due to thermal, chemical, radiation effect)
❖ initiation:
free radical reacts with monomer
❖ propagation:
the new free radical reacts with other monomer
❖ termination:
dead polymer chain producting, which is not capable of further
addition

 factors, which can determinate the

properties
❖ molecular weight
the chain length can be different: average molecular weight
❖ degree of chain branching
generally linear polymers
modified: chain transfer
❖ or cross-linking
with cross-linking agents (with two double bonds) to the
monomer

 factors, which can determinate the

properties
❖ molecular weight
the chain length can be different: average molecular weight
❖ degree of chain branching
generally linear polymers
modified: chain transfer
❖ or cross-linking
with cross-linking agents (with two double bonds) to the
monomer

 ionic addition

❖ impression materials
ring opening polymerisation of imines
❖ resin matrix composite
ring opening polymerisation of oxiranes and
closely related siloranes

condensation polymerisation
 Polymerisation
Condensation
Addition
❖ A+B=C+d
❖ A+B=C

❖ “A”: reactive species ❖ “A”: organic acid

❖ “B”: monomer ❖ “B”: alcohol

❖ “C”: esther
❖ “C”: larger reactive species
❖ “d”: bioproduct (water)



 each reacting molecules have at least two reactive

groups, capability to further reactions

two monomers,
with reactive
groups: X, Y

regular copolymer: M1 and M2 monomers in sequence

along the chain
❖ trifunctional monomer
chain branching and cross-
linking producing
❖ homopolymer
only one monomer with two
reactive groups

 physical changes during polymerisation

❖ phase changes

❖ temperature
changes

❖ dimensional
changes
http://cdn.tinybuddha.com/wp-content/uploads/
2010/07/Changing-Seasons.jpg




 phase changes
❖ monomers are generally gases or liquids at normal pressure
and temperature

❖ mixing with inert fillers (glass powder) to form pastes

❖ viscosity increasing

❖ rigidity increasing

❖ the monomer conversion declines

❖ diffusion of monomer is slow due to viscosity

❖ small concentration of residual monomer

❖ dental polymers are generally amorphous

 temperature changes
❖ usually exothermic
❖ marked increase in temperature of the
polymerizing material

 industrial polymers
❖ suspension polymerisation

❖ dissolve in solvent, or in water, the polymer is powder with

solvent beads

❖ injection moulding

❖ moulding into shape under pressure, softening with heat

❖condensation polymers
❖cured in bulk, absence of water or solvent
❖stopping with cooling in case of small amount of monomer
❖partially polymerised monomer moulding
❖polymerisation is complete in moulding stage

 dental polymers

❖ smaller amount
❖ in bulk
❖ in situ (in the mouth)
❖ carefully!!!!!!,
damage of the pulp

http://3.bp.blogspot.com/-LwTpOZUBKaQ/T1Sr4j3m_8I/AAAAAAAACPQ/
POsPq2klQKQ/s1600/
Mandibular+Implant+Verification+Jig+Fabrication+in+Mouth+Rachel+Dahler+
%284+of+4%29.jpg

 dimensional changes
❖contraction (addition, condensation)

❖Polymethylmethacrylate (PMMA): 21%

❖options to reduce

❖blending the monomer with inert material (glass

powder, or polymer)
❖overfilling of the mould
❖polymerising under pressure

structure and properties

factors, which control the structure and
properties

❖ molecular structure of the repeating units

❖ molecular weight or chain length
❖ degree of chain branching
❖ presence of cross-linking, cross-link
density
❖ presence of plasticizers or fillers

crystalline polymers amorphous polymers

(dental)
❖ glass transition
temperature (Tg) ❖ glass transition
temperature (Tg)
❖ melting temperature
(Tm) ❖ molecular motions
become, the whole
chains are able to
move

❖ softening temperature






methods of fabricating
polymers
 thermoplastic thermosetting
polymers resins

softening by heating, generally condensation polymers

re-hardening by cooling partially polymerised before moulding
❖ injection moulding viscous liquide

❖ vacuum forming heating

❖ blow moulding polymerisation

highly cross-linked polymers

 in dentistry

Self-curing, chemopolimerisation dough moulding

❖ blend the monomer with inert filler ❖ powdered polymer beads with
to form paste initiator

❖ two halves ❖ mixing with monomers to

form dough
❖ initiator ❖ packing to preform mould,
heating
❖ activator

❖ mixing

❖ polymerisation is completed

denture base polymers

 natural polymers
❖ prior 1940: vulcanite
highly cross-linked natural rubber
❖ difficult to pigment
❖ uptake of saliva

synthetic polymers
1903: laccain –replacement of sellak
1907: bacelit
1920: vinil, acrylacid and stirol –new
polymers
1936: metacrylic acid methylester =

acrylate

 dough moulding method

❖ fabricating in two-part mould

❖ wax trial denture in the mould
❖ boiling out the wax
❖ mould-sealing agent
❖ acryl dough insertion
❖ heat curing, or at room
temperature curing

other methods:
❖ injection
moulding
❖ pourable resin
technique

http://elitedentallabcoop.com/wp-
content/uploads/2014/02/Complete-
Denture.jpg

requirements of denture base

polymers
 physical properties

like a natural oral tissues

❖ Tg (glass transition temperature) high enough to
prevent softening during use
❖ good dimensional stability
❖ low value of specific gravity: light
❖ high value of thermal conductivity to avoid burning
❖ radiopaque

 mechanical properties

❖ high value of modulus of elasticity, elastic limit

❖ sufficient flexural strength
❖ high fatigue life, fatigue limit
❖ high impact strength
❖ sufficient abrasion resistance

 chemical biological
properties properties

❖ chemically inert ❖ non-toxic

❖ insoluble in oral fluids ❖ non-irritant
❖ not absorb water,
❖ impermeable to oral
saliva fluids

 other properties

❖ relatively
inexpensive
❖ long shelf life
❖ easy to manipulate
❖ easy to repair

http://static.neatorama.com/images/
2013-11/denture-compact-mirror-1.jpg

acrylic denture base materials

 type 1 and 2
powder:

❖ polymethylmethacrylate beads up to 100 µm

❖ made by suspension polymerisation

❖ methylmethacrylate monomer and initiator are

suspending in water as droplets

❖ heating

❖ polymethylmethacrylate beads

❖ drying to free flowing powder

 powder
❖ polymethylmethacrylate is a
clear, glass-like polymer

❖ incorporate pigments,
opacifiers

❖ small fibres to veined

appearance
http://www.ledenturo.ca/images/
content/services/full-denture-1.jpg

 liquid

❖ clear
❖ colourless
❖ low-viscosity
❖ boiling point 100,3 °C

http://cdn.shopify.com/s/files/1/0205/1890/
products/miracryl-denture-
base_liquid_grande.jpg?v=1363203791

 liquid (dark brown bottle)

❖ methylmethacrylate (MMA) monomer

❖ cross-linking agent (improve the physical
properties)
❖ inhibitor (shelf life)
❖ activator (self-curing, or autopolymerizing)

heat curing materials

 mixing

❖ powder and liquid to form dough

❖ MMA shrinkage is 21%

❖ reducing

❖ high powder/liquid ratio

❖ granular porosity: dry mix

❖ ideal ratio: 2,5:1

❖ 5-6% shrinkage

 ❖ after mixing “sandy”

consistency

❖ sticky
❖ strings of material sticking doughing
to the spatula time
❖ dough stage

❖ tough, rubbery
working time
❖ hard

❖ dough take to the mould with excess

❖ trial closure
❖ open
❖ closing under pressure
❖ dough flows into every part
❖ reduction of the shrinkage (excess
dough apply)
❖ not too thick the baseplate
❖ contraction porosity: insufficient
pressure or dough amount

http://pocketdentistry.com/wp-content/uploads/
1008/
B9781437724189000198_f019-003b-978143772418
91.jpg

 injection moulding

❖ dough forced into mould

❖ sprue hole, vent hole in the mould
❖ wave of curing propagates from the sprue

 curing-popular method

❖ flask take to water bath or air oven

❖ heat the flask for 7 hours at 70 °C
❖ most of conversion of monomers
❖ 3 hours 100 °C
❖ complete conversion in thinner area

❖ cooling to room temperature slowly: reduce the

internal stress due to thermal expansion
❖ deflasking

autopolymerizing materials
❖ powder and liquid mixing
❖ very rapid
❖ gradual increase in
polymerisation
viscosity (physical,
chemical changing) ❖ inferior mechanical
❖ dough stage (very rapidly) properties

❖ short working time ❖ high residual monomer

content
❖ no trial closure

❖ hard
repairing, relining

 pourable resins

❖ very fluid consistency: low powder/liquid ratio

❖ poured into hydrocolloid mould
❖ at room temperature

advantages: disadvantages:
rapid high residual monomer
easy removing from mould inferior mechanical properties
little finishing necessary possibility of distortions

 light activated materials

content:
❖ premixed in light-
❖ urethane dimethylacrylate proof sachet
monomer
❖ in specialist oven
❖ sub-micron particles of
silica ❖ athmospheric
pressure
❖ polymethylmethacrylate
beads ❖ surface coating with
non-reactive barrier
❖ organic filler
hollow denture base or
❖ light sensitive initiator obturators
❖ activator

modified acrylic alternative

materials polymers

❖ incorporation of
elastomers ❖ polycarbonates

❖ carbon fibre ❖ polyamid

insertion ❖ vinyl polymers
❖ incorporate
radiopacity ❖ vulcanite

denture lining materials

 improving the fit of the denture

lining of self-curing resin

whole of the denture base
❖ traumatized soft tissue
can be replaced with fresh ❖
hard reline materials
heat curing acrylic resin ❖
tissue conditioners
❖
soft lining materials

hard reline materials

 method

❖ grinding the fitting surface

❖ powder, liquid mixing
❖ mix given into the fitting surface
❖ insert into the mouth
❖ closing into gentle contact
❖ material will be rubbery
❖ removing from the mouth
❖ placing to warm water with/without pressure

 properties
❖ irritant in direct contact
❖ petroleum jelly protection
❖ increased dimensional stability
❖ porous due to air inclusions during mixing
❖ easily contaminated

❖ little control over

criticizm the thickness

❖ occlusal errors

 tissue conditioners

❖ soft denture liners

❖ plastic flow for 24-36 hours after mixing

❖ indications:

❖ after soft tissue trauma (ill-fitting denture) before new

denture

❖ after surgery: reduce the pain, and traumatisation

❖ immediate procedure after extraction

❖ functional impression material

 requirements

❖ soft during use

❖ resilient
❖ permanent
deformation

 composition

❖ powder, liquid
❖ alcohol
7.5-40%
❖ pigments

 method

❖ chairside

❖ freshly mix material

take to the fitting
surface

❖ take in the mouth

❖ repeat after 2-3 days

 temporary soft lining materials

❖ similar to the tissue conditioners

❖ powder, liquid

❖ retain their softness for longer (1-2 month)

❖ after 2 month hard, rough, easily colonized

❖ indication:

❖ no option the tissue conditioner

❖ temporary improving the fit

 permanent soft lining materials

❖ patient, not-tolerate the hard base…..

❖ permanently soft

❖ elastic

❖ adhere to the denture base

❖ non-toxic

❖ non-irritans

❖ difficulty contaminated

temporary crown and bridge

materials
❖ immediate temporary coverage following tooth preparation for crown
or bridges

❖ usual technique: SCUTAN method

❖ impression taking before preparation with alginate or silicone

❖ preparation

❖ mixed temporary crown material place to the impression

❖ place in the mouth

❖ after initial setting removing

❖ hardening outside the mouth

❖ Adaptation of a prefabricated plastic crown to the tooth

❖ temporary cementing with temporary cement (zink-oxide eugenol)

 requirements

❖ non-injurious to oral tissues

❖ not so high temperature rising

❖ small setting contraction

❖ sufficient working time for mixing, placement into the impression, seating
into the mouth

❖ easy removal in rubbery stage without distortion

❖ rapid hardening outside the mouth

❖ strong, hard

❖ tooth-coloured

 properties

❖ setting characteristic:

❖ in rubbery stage removing from the mouth

❖ take to hot water for a few seconds

❖ visible light activation

❖ not remain in the mouth during the setting

because of shrinkage, exothermic process

❖ maximum temperature is after 1-2 minutes of the

rubbery phase

❖ biocompatibility:
❖ using petroleum jelly as protective material
❖ mechanical properties:
❖ can be very thin layer
❖ appearance:
❖ range of shades

Surface modification
 Carbide cutters

https://www.keverocsor.hu/fogaszati-termekek/
fogtechnika_134/
egyenesdarabba_valo_235_mm_eszkozok_180/kemenyfem-
 Carbide cutters

http://www.doktormarket.hu/frezer-korrekcios-keszlet-fogtechnikai-
fogsorok-korrekciojahoz-12-db-kemenyfem-1468
 sanding disc

https://www.mwdental.hu/dimo-279287---csiszolokorongok-
csiszolopapir-19473-d-pg-shop.html
sanding disc

https://www.mwdental.hu/lisko-s-korongok-279281---
csiszolokorongok-csiszolopapir-19473-d-pg-shop.html
 rubber polisher

https://www.keverocsor.hu/forgoeszkozok_175/
egyenesdarabba_valo_235mm_eszkozok_176
 rubber polishers for mandrell

https://www.mwdental.hu/eve-univerzalis-polirozok-
szereletlen-279373---gumipolirozok-19489-d-pg-shop.html
https://www.mwdental.hu/mandrellek-279301---
mandrellek-19475-d-pg-shop.html
https://www.mwdental.hu/univerzalis-polirozo-paszta-279515---
polirozo-pasztak-habkopor-19493-d-pg-shop.html
polishing brush
 https://frdental.hu/blog/top-tema-hirek/teljes-
kiveheto-mufogsor.html

http://www.yourdent.hu/
fogmegtartas/teljes-
kiveheto-
fogpotlas-933.html
Allergy
 Literature:
❖ J.A. Bartoloni, D. F. Murchison, D.T Wofford, N. K. Sarkar: Degree of conversion in denture base materials for
varied polymerization techniques. Journal of Oral Rehabilitation 27:488-493 (2000)
❖ Canan Bural, Eskin Aktas, Günnur Deniz, Yesim Ünlücerci, Nilgün Kizilcan, Gülsen Bayraktar: Effect of post-
polymerization heat-treatments on degree of conversion, leaching residual MMA and in vitro
cytotoxicity of autopolymerizing acrylic repair resin. Dental Materials 27:1135-1143 (2011)
❖ Gottfried Schmalz, Dorthe Arenholt-Bindslev: Biocompatibility of Dental Materials. Springer, (2009)
❖ Roland Franz, Rainer Brandsch: Migration of acrylic monomers from methacrylate polymers – establishing
parameters for migration modelling. Packaging Technology and Science 26:435-451 (2013)
❖ Ian Kimber, Mark A. Pemberton: Assessment of the skin sensitising potency of the lower alkyl methacrylate
esters. Regulatory Toxicology and Pharmacology 70:24-36 (2014)
❖ Mark A., Pemberton, Barbara S. Lohmann: Risk assassment of residual monomer migrating from acrylic
polymers and causing Allergic Contact Dermatitis during normal handling and use. Regulatory Toxicology
and Pharmacology 69:467-475 (2014)
❖ Yi-Tsz Lin, Shih-Wei Tsai, Ching-Wen Yang, Yu-Hsian Tseng, Chia-Yu Chu: Allergic contact dermatitis caused by
acrylates in nail cosmetic products: Case reports and review of the literatures. Dermatologica Sinica
36:218-221 (2018)

 Prosthetic appliances Artificial fingernails,

nail warnish

❖Heat, or auto-polymerizable materials:

PMMA

❖Photo-polymerizable materials:
PMMA,
UDMA-urethane dimethacrylate,
EGDMA- ethylene glycol dimethacrylate

❖Microwave-polymerizable materials:
PMMA,
UDMA-urethane dimethacrylate,
EGDMA-ethylene glycol dimethacrylate




















plastics made by technicians
❖ longer polymerization time,
❖ other effects (heat, pressure) are always used to improve the
polymerization rate.
❖ Bartoloni et al. (percentage of polymerization) (2000):
❖ Traditional heat-activated (74 ° C, 9 hours): 92.71%
❖ In the microwave oven (500W, 3 min): 92.63%
❖ Soldered (100 ° C, 20 min): 90.87%

Chair side prostheses

❖ Follow the manufacturer's instructions!
❖ polymerization type
❖ temperature
❖ ratio of ingredients
❖ polymerization time
❖ surface structure
❖ Canan Bural et al. (MMA) (2011)

 Canan Bural, Eskin Aktas, Günnur Deniz, Yesim Ünlücerci, Nilgün Kizilcan, Gülsen Bayraktar: Effect of post-
polymerization heat-treatments on degree of conversion, leaching residual MMA and in vitro cytotoxicity of
autopolymerizing acrylic repair resin. Dental Materials 27:1135-1143 (2011)
 DC: degree of conversion

Canan Bural, Eskin Aktas, Günnur Deniz, Yesim Ünlücerci, Nilgün Kizilcan, Gülsen Bayraktar: Effect of post-
polymerization heat-treatments on degree of conversion, leaching residual MMA and in vitro cytotoxicity of
autopolymerizing acrylic repair resin. Dental Materials 27:1135-1143 (2011)
 ❖ Depending on the type of polymerization, residual
monomers and other substances may be dissolved
(MMA, formaldehyde)
LOCAL Adverse Effect: DENTURE STOMATITIS
❖ The carcinogenic and embryotoxic effects of MMA
have not been demonstrated and did not increase the
incidence of tumors in the long term.
❖ PMMA can be allergic, MMA and initiator: dibenzoyl
peroxide and EGDMA are allergic!
❖ Penetrates into latex and polyvinyl gloves!
❖ Ventilation to prevent inhalation!
❖ For allergy replacement: Polyvinyl

Plastic Allergy Symptoms:

❖burning sensation of the oral mucosa near to

dentures
❖reddish discoloration
❖dry mouth
❖swelling of the mouth, lips
❖eyelid oedema
❖itchy rashes around the mouth

Inflammation, allergy
Thank you for your attention:)))

https://www.life.hu/csalad/20190801-egyszerre-remiszto-es-vicces-fotok-kisbabakrol-akiknek-fogsora-
lett.html