Polymers

Polymer: A chemical compound consisting of a large organic molecule

(macromolecule) formed by the union of many smaller repeating units
(mers).
Monomer: It is a single molecule from which the polymer is constructed.
It is a chemical compound that is capable of reacting to form a polymer.
Mer: The term used to designate the repeating unit or units in a polymer
chain; thus mers are the “links” in the chain.

Polymerization: Chemical reaction in which monomers of a low

molecular weight are converted into chains of polymers with a high
molecular weight. The polymerization is exothermic reaction.

Monomer+ Monomer+ Monomer+ Monomer polymerization Mer Mer Mer Mer

Copolymers: Polymer made of two or more monomer species and

identical monomer units (mers) occurring in relatively long sequences
along the main polymer chain. “copolymer when two or more different monomer
present in same polymer”

Copolymerization is used to improve the physical properties of the resulting resin.

Crosslinked: A difunctional or multifunctional monomer that forms a

link between two polymer chains. Crosslinked polymers have many such
crosslinks between neighboring chains such that a three-dimensional
interconnected polymer network result.

Degree of polymerization (D.P): Is specified by the total number of

repeated units in the chain of the polymer. The higher the degree of
polymerization the better will be the physical properties.

Glass transition temperature (Tg): The temperature at which

macromolecule molecular motion begins to force the polymer chains
apart. Thus, polymeric materials soften when heated above this
temperature (It is the temperature was the polymers leave the rigid state
and transfer into rubber like phase).

Factor control polymer properties:

1. Chemical composition of the polymer: This depends on types of

monomers and its structure.

e.g.
CH2—CH---R-vinylpolymer
when R=H polyethylene, the repeating unit is CH2 group. Polyethylene is
hydrophobic semicrystalline polymer.
But when R=OH the (polyvinyl alcohol) hydrophilic, water soluble
polymer with gelling properties.

2. Topology of polymer chain:

•Linear polymer. A-A-A-A

A-A-A

• Nonlinear (branched) polymer. A-A-A-A-A-A

A-A-A

• Cross linked polymer (polymer network). The cross linking (permanent connection
between the polymer chains) restricting the motion of the chains and improve
rigidity of polymer. A-A-A-A-A-A-A

A-A-A-A-A-A-A-A

A-A-A-A-A-A-A

The advantages of cross-linking agents:

1. Improve hardness and stiffness.

2. Increase wear and solvent resistance.

3. Increase crazing resistance.

4. Increase brittleness.

5. Increase thermal resistance.

6. Decrease water sorption and solubility.

3. Monomer distribution in the polymer chain:

A. Homo polymers (one type of monomer) (linear or branched).

A-A-A-A-A-A

B. Co polymers (2 or 3 types of monomers) it is ether:

• Random copolymer: No sequential order exists among the two or more mer units
along the polymer chain.

…ABBABABAAABAAAABABBBBABAAAABABABB…

• Block copolymer: Identical monomer units occur in relatively long sequences

(blocks) along the main polymer chain.

…AAAAABBBBBBBAAAABBBBBBBAAABBBAAAA…

• Alternating copolymer: …..ABABABABAB…..

• Graft or branched copolymer: Sequences of one type of mer unit (B) are “grafted”
onto a backbone chain of a second (A) type of mer unit to form a branched
configuration.

4. Polymer molecular weight (Mw). Mw of polymer molecules= the Mw of the mers

x number of mers. Molecular weight may range from thousand to millions of
molecular weight units depending on preparation conditions. Molecular weight of
polymers plays an important role in determining its physical properties. Most
polymers have a wide range of Mw and so vary widely in their properties. The higher
the Mw the higher the softening and melting point and the stiffer the plastic. The
higher the Mw of polymer made from a single monomer, the higher the degree of
polymerization. The strength of the resin increases with the increasing of the degree
of polymerization until a certain Mw is reached. Above this there is no change.

5. Supra molecular structure (molecular organization).

A. Amorphous polymers (coiled irregular) random Shape of polymer chains.

B. Semi crystalline polymer: domains with regular (crystalline) structure acting as

special type of cross - links.

Polymers used in dentistry:

• Natural polymers. e.g. gutta percha.

• Synthetic polymers (prepared by polymerization reaction).

Application of polymers in dentistry:

1. Prosthodontics: denture bases, denture teeth, soft liners, custom trays, impression
materials, cementing materials, maxillofacial prostheses …….

2. Operative Dentistry: dentin bonding agents, cavity fillings, resin and glass-
ionomer cements, veneers…..

3. Orthodontics: brackets, bracket bonding resins and cements, and spacers.

4. Endodontics: gutta-percha points, root canal sealants, and rubber dams.

5. Equipment: mixing bowls, mouth guards , protective eyewear….

The types of polymerization reaction:

1. Condensation polymerization.

2. Addition polymerization.

1. Condensation polymerization: usually more than one type of monomer is used;

The condensation reaction progress by the same mechanism as chemical reaction
between two or more simple molecules. The reaction produces by products such as
water, halogen acids and ammonia or alcohol.

2. Addition polymerization: most dental resins are polymerized by additional

polymerization which simple involves the joining together of monomer molecules
to form polymers chain. In this type of reaction, no by product is obtained. There is
no change in composition during addition polymerization. It's formed from smaller
units or monomers without change in composition, the monomer must have an
unsaturated group in its structural formula for covalent bond with another molecule.

The additional reaction take place in 3 stages as follow:

1. Induction stage.

2. Propagation stage.

3. Termination stage.

1. Induction stage: Two processes control the induction stage (activation and
initiation). For an addition polymerization process to begin, a source of free radicals
(R•) is required. Free radicals can be generated by the activation of radical-producing
molecules like heat, visible light and chemical agents.
Free radicals: Are very reactive chemical species that have unpaired electron; the
free radicals are produced by reactive agents called initiators. The free radical reacts
with a monomer and initiates the polymerization process.

Initiators: Are molecules which contain one relatively weak bond which is able to
undergo decomposition to form two reactive species (free radicals). The
decomposition of bond of initiator needs source of energy (activator) such as heat,
light and chemical activator.

Initiator which is used extensively in dental polymers is Benzoyl peroxide.

Decomposed and free radicals are formed.

R ————R + external energy 2 R• (R= represent any organic molecular)

initiator

free radicals R• + M R-M• Free radicals monomer reactive free radical species

The initiation reaction is an addition reaction producing another active radical

species which is capable of further reaction (addition of free radical on the double
bond of monomer)

The initiation period depends on the purity of the monomer and the temperature of
the reaction. Any impurities present that are able to react with activated groups can
increase the length of this period (induction period). The higher the temperature, the
more rapid the formation of free radicals and consequently the shorter the induction
period.

2. Propagation stage: The initiation stage is followed by the rapid addition of other
monomer molecules to the free radical and shifting of free electron to the end of
growing chain, this called propagation stage.

R—M• + M R—M—M•
R—M—M• + M R—M—M—M•

R—M—M—M• + M R—M—M—M—M•

3. Termination stage: The growing chain is stopped. Termination occurs when

monomer units are used up or free radical is finished by reaction. Chain reaction can
be terminated either by reaction of two growing chains to form one dead chain or by
reaction of growing chains with molecules of initiation, dead polymer, impurity or
solvent if present.

R—M—M—M• + R—M—M—M• R—M—M—M—M —M—M— R

Inhibitor: It is chemical materials added to prevent or delay polymerization during

storage and in order to provide enough working time and decrease sensitivity to
ambient light like hydroquinone.

The following factors inhibit the polymerization:

1. Any impurity in the monomer that can react with free radicals or with any
activated growing chain to prevent further growing.

2. The addition of small amounts of hydroquinone to the monomer.

3. The presence of oxygen also causes retardation of polymerization reaction

because the oxygen reacts with free radicals and so the degree of polymerization is
decreased.

Plasticizer: These are substance added to the resins to:

1. Decrease the brittleness of the polymer.

2. Increase the solubility of the polymer in the monomer.

3. It decreases strength, hardness and softening point it is used to prepare flexible

polymer.
Classification of polymer according to thermal response:

1. Thermoset polymer.

2. Thermoplastic polymer.

Thermosetting polymer or resins: Thermosetting polymers undergo a chemical

change during the setting reaction and become permanently hard when heated above
the temperature at which they begin to polymerize; they do not soften again on
reheating to the same temperature. They are usually cross linked in this state, and
thus, they are insoluble and will not melt. Instead, they decompose if heated to a
high enough temperature. Thermosetting polymers generally have superior abrasion
resistance and dimensional stability compared with thermoplastic polymers.

Thermoplastic polymer or resins: They soften when heated above the glass
transition (The resin can be shaped and molded) and upon cooling it will harden; this
cycle can be repeated almost indefinitely. The setting.

reaction is reversible because of the relatively weak bonds among the molecular
chains. Thus, in contrast to thermosetting resins, thermoplastic resins can be melting
and are usually soluble in organic solvents and have better flexural and impact
properties. e.g. flexible denture.

Denture base resin material

Various materials have been used to construct dentures like cellulose products,
phenol- formaldehyde, vinyl resins and vulcanite, however they have suffering from
a variety of problems. Acrylic resin (polymethyl methacrylate) (PMMA) is now the
material of choice to use as denture base material because it is easy to process and
use, cheep and good esthetic. Even so it is not ideal in all respects.

The ideal requirements of denture base material represents by the followings:

1. Natural appearance. 2. High strength, stiffness, hardness and toughness.

3. Dimensionally stability.

4. Tasteless, odorless, non toxic and none irritating the oral tissue.

5. Insoluble in saliva or other fluids taken in to the mouth.

6. Good retention to polymer, porcelain and metals.

7. Easy to fabricate and Easy to repair. 8. Good shelf life. 9. Low density.

10. Accurate reproduction of surface details. 11. Resistance to bacterial growth.

12. Good thermal conductivity. 13. Radiopacity. 14. Easy to clean.

15. Inexpensive to use. 16. The softening temperature should be higher than
mouth temperature.

The Types Of Denture Base Resin:

• Heat cure denture base resin, set by heat a. water bath b. microwave

• Light cure denture base resin.

• Cold cure, self-cure denture base resin

Classification of denture base materials

According to the Type of Materials

• metallic e.g. Cr/Co denture base

• nonmetallic materials e.g. poly (methyl methacrylate).

According to the Method of Polymerization

• Addition polymers, e.g. poly (methyl methacrylate)

• Condensation polymers, e.g. nylon.

According to their Thermal Response

• Thermoplastic, e.g. polyvinyl acrylics and polystyrene.

• Thermosetting, e.g. poly (methyl methacrylate).

According to the Method of Activation

• Thermal; e.g. poly (methyl methacrylate).

• Microwave; e.g. poly (methyl methacrylate).

• Catalyst; e.g. poly (methyl methacrylate).

• Visible light activated; e.g. poly (methyl methacrylate).

According to the Dispensing System

• Power and liquid system, e.g. heat-cure and self-cure acrylic resins.

• Sheets and ropes: (Single component system), e.g. light activated denture base
resins.

• Gel type, e.g. vinyl acrylics