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Polymers and Polymerization in Dentistry

Polymers and Polymerization in Dentistry Dr Amal Ezzeldin Fahmy Assistant Professor of Dental Biomaterials Faculty Of

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

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Terminology

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

Poly

Mono = single

Mer

Oligo

= many

= unit

=several

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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

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Ethylene DR Amal Ezz EL Din H   H     H H H  

Ethylene

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H

 

H

   

H

H

H

 

C

C

C

C

C

 

H

H

H

H

H

POLY

Ethylene

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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

combine to form high mol. Wt . polymers • It requires the presence of covalent bonds

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Applications of Polymers in Dentistry

Applications of Polymers in Dentistry • Denture base materials • ·Acrylic teeth(Artificial) DR Amal Ezz EL

Denture base materials

Applications of Polymers in Dentistry • Denture base materials • ·Acrylic teeth(Artificial) DR Amal Ezz EL
Applications of Polymers in Dentistry • Denture base materials • ·Acrylic teeth(Artificial) DR Amal Ezz EL

·Acrylic teeth(Artificial)

Applications of Polymers in Dentistry • Denture base materials • ·Acrylic teeth(Artificial) DR Amal Ezz EL
Applications of Polymers in Dentistry • Denture base materials • ·Acrylic teeth(Artificial) DR Amal Ezz EL

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Applications of Polymers in Dentistry

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

Soft Linings:

plasticised polymers, higher methacrylates and silicone rubbers.

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Applications of Polymers in Dentistry

Cements: polyacrylic acid is a constituent of zinc polycarboxylate cements and glass-ionomer cements.

· ·
·
·
polycarboxylate cements and glass-ionomer cements. · · Polymeric crown and bridge materials Die materials: filled
polycarboxylate cements and glass-ionomer cements. · · Polymeric crown and bridge materials Die materials: filled

Polymeric crown and bridge materials

Die materials: filled polymer

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Applications of Polymers in Dentistry cont.

Applications of Polymers in Dentistry cont. Removable tooth movement devices Orthodontic retainers DR Amal Ezz EL

Removable tooth movement devices Orthodontic retainers

Applications of Polymers in Dentistry cont. Removable tooth movement devices Orthodontic retainers DR Amal Ezz EL

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Applications of Polymers in Dentistry cont. Removable tooth movement devices Orthodontic retainers DR Amal Ezz EL

Applications of Polymers in Dentistry

Applications of Polymers in Dentistry Impression materials: e.g agar and alginates polysulphide, silicone polyether

Impression

materials:

e.g agar and alginates polysulphide, silicone polyether elastomers

in Dentistry Impression materials: e.g agar and alginates polysulphide, silicone polyether elastomers DR Amal Ezz EL
in Dentistry Impression materials: e.g agar and alginates polysulphide, silicone polyether elastomers DR Amal Ezz EL
in Dentistry Impression materials: e.g agar and alginates polysulphide, silicone polyether elastomers DR Amal Ezz EL
in Dentistry Impression materials: e.g agar and alginates polysulphide, silicone polyether elastomers DR Amal Ezz EL
in Dentistry Impression materials: e.g agar and alginates polysulphide, silicone polyether elastomers DR Amal Ezz EL

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Applications of Polymers in Dentistry

Mouth guards (Athletic mouth protectors)

Applications of Polymers in Dentistry • Mouth guards (Athletic mouth protectors) DR Amal Ezz EL Din
Applications of Polymers in Dentistry • Mouth guards (Athletic mouth protectors) DR Amal Ezz EL Din

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Applications of Polymers in Dentistry

Applications of Polymers in Dentistry DR Amal Ezz EL Din • Restorative materials: composite materials •
Applications of Polymers in Dentistry DR Amal Ezz EL Din • Restorative materials: composite materials •
Applications of Polymers in Dentistry DR Amal Ezz EL Din • Restorative materials: composite materials •

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Restorative materials:

composite materials

Polymers used in the so-called adhesive techniques

natural resins such as copal or rosin Varnishes contain

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

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Structure of polymers based on spatial arrangement of monomer molecules

Three basic structures:

Linear

Branched

Cross-linked

of monomer molecules • Three basic structures : • Linear • Branched • Cross-linked DR Amal
of monomer molecules • Three basic structures : • Linear • Branched • Cross-linked DR Amal
of monomer molecules • Three basic structures : • Linear • Branched • Cross-linked DR Amal
of monomer molecules • Three basic structures : • Linear • Branched • Cross-linked DR Amal
of monomer molecules • Three basic structures : • Linear • Branched • Cross-linked DR Amal
of monomer molecules • Three basic structures : • Linear • Branched • Cross-linked DR Amal

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Structure of Polymers

Structure of Polymers In the branched polymers There are side chains DR Amal Ezz EL Din

In the branched polymers There are side chains

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Structure of polymers

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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

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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.

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Based on the type of polymerization reaction

I-ADDITION POLYMERIZATION

II-CONDENSATION POLYMERIZATION

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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

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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

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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

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Stages of Addition polymerization

Stages of Addition polymerization • Initiation • R 1 ˙ + M • Propagation • R

Initiation

R 1 ˙ + M

Propagation

R 1 M˙ + M

R 1 MM˙+M

Termination

R 1 Mn˙ + R 1 Mm˙

R 1

Termination • R 1 Mn˙ + R 1 Mm˙ R 1 M˙ R 1 MM˙ R

R 1 MM˙ R 1 MMM˙

• R 1 Mn˙ + R 1 Mm˙ R 1 M˙ R 1 MM˙ R 1
• R 1 Mn˙ + R 1 Mm˙ R 1 M˙ R 1 MM˙ R 1

R 1 Mn+ R 1 Mm

• R 1 Mn˙ + R 1 Mm˙ R 1 M˙ R 1 MM˙ R 1

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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

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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)

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Polysulphide impression setting rxn

Polysulphide impression setting rxn DR Amal Ezz EL Din

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Condensation silicone

Condensation silicone DR Amal Ezz EL Din

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Copolymerization

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

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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

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

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DR Amal Ezz EL Din Plasticizers • They are substances added to the resins :
DR Amal Ezz EL Din Plasticizers • They are substances added to the resins :

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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

Plasticizers effects

Added to stiff, glassy uncross-linked polymers Lowers glass transition temperature (Tg) Become

rubber-like,

Flexible

less brittle

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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)

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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

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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

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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

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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)

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Acrylic plastics for Denture Bases

Powder-liquid type most popular

Polymer= PMMA

Principle component of powder

Present as beads or pearls

Wide range of shades available

Liquid =MMA

Highly volatile

Always supplied in a dark bottle

BP=100.3

Immiscible in water

Highly flammable

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H

CH 3

C=

C

H

COOH

H CH 3 C= C H COOH Methyl Acrylic acid DR Amal Ezz EL Din H

Methyl Acrylic acid

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H

CH 3

C = C

H

COOCH 3

Methyl

Methacrylate

Acrylic denture base polymer

Presentation: - powder-liquid

- gels

-
-

sheets or blanks

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

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Processing

Processing DR Amal Ezz EL Din
Processing DR Amal Ezz EL Din
Processing DR Amal Ezz EL Din
Processing DR Amal Ezz EL Din

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Another example for free radical addition polymerization responsible for setting of composite resins

O

O

CH

CH 2 =C-C-O-CH 2 CH-CH 2 O

=C-C-O-CH CH-CH O

=C-C-O-CH CH-CH O

CH

2 2

2 2

2 2

CH

CH 3

3

OH

OH

CH CH 3 3 -C- -C- -C- CH CH 3 3
CH
CH
3 3
-C-
-C-
-C-
CH
CH
3 3

O

O

OCH CHCH O-C-C=CH

OCH 2 CHCH 2 O-C-C=CH 2

OCH CHCH O-C-C=CH

2 2

2 2

2 2

OH

OH

CH

CH 3

3

Bis GMA

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RING OPENING POLYMERIZATION

RING OPENING POLYMERIZATION WorkingWorking WorkingWorking CastCast withwith CastCast withwith RemovableRemovable

WorkingWorking

WorkingWorking

CastCast withwith

CastCast withwith

RemovableRemovable

RemovableRemovable

DiesDies

DiesDies

RemovableRemovable RemovableRemovable DiesDies DiesDies EdentulousEdentulous EdentulousEdentulous CastCast CastCast
RemovableRemovable RemovableRemovable DiesDies DiesDies EdentulousEdentulous EdentulousEdentulous CastCast CastCast

EdentulousEdentulous

EdentulousEdentulous

CastCast

CastCast

OrthodonticOrthodontic

OrthodonticOrthodontic

ModelModel

ModelModel

WorkingWorking

WorkingWorking

CastCast

CastCast

The ring structure is the structure is opened and cross linking occur

e.g. polymerization of polyethylene rubber base impression materials it involves opening of ethylene imine ring

Epoxy resins used to form polymeric dies

O

imine ring • Epoxy resins used to form polymeric dies O CH2_CH2 RemovableRemovable RemovableRemovable DieDie

CH2_CH2

ring • Epoxy resins used to form polymeric dies O CH2_CH2 RemovableRemovable RemovableRemovable DieDie withwith DieDie

RemovableRemovable

RemovableRemovable

DieDie withwith

DieDie withwith

WaxedWaxed InlayInlay

WaxedWaxed InlayInlay

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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

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silicone rubber

materials • Vinyl terminated polydimethyl siloxane+ silane terminated siloxane HPTCL DR Amal Ezz EL Din silicone
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ethylene H C= H CH C COOH acrylic acid DR Amal Ezz EL Din

ethylene

H

ethylene H C= H CH C COOH acrylic acid DR Amal Ezz EL Din

C=

H

CH

C

COOH

acrylic acid

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