Addition polymerisation

Addition polymerizations involve the addition of

a reactive species with a monomer to form a larger
reactive species which is capable of further
addition with monomer

John F. McCabe, Applied Dental Materials Ninth E

Activation
This involves decomposition of the peroxide

initiator using either thermal activation

(heat), chemical activators or radiation of a
suitable wavelength .For benzoyl peroxide
the activation reaction is represented by
the equation
R O O R 2RO
where R represents any organic molecular
grouping.

John F. McCabe, Applied Dental Materials Ninth E

Initiation
The polymerisation reaction is initiated when the

radical, formed on activation, reacts with a

monomer molecule. This is illustrated for the
specific case of the benzoyl peroxide radical and
the methacrylate monomer
RO + M RO M
where the symbol M represents one molecule of
monomer.
It can be seen from the above equation and from
Fig. 12.4 that the initiation reaction is an addition
reaction producing another active free radical
species which is capable of further reaction.

John F. McCabe, Applied Dental Materials Ninth E

Propagation
Following initiation, the new free radical is

capable of reacting with further monomer

molecules. Each stage of the reaction
produces a new reactive species capable of
further reaction, as illustrated in the
following equations:
RO M + M RO M M
RO M M + M RO M M M
RO M M M + M RO M M M
M

John F. McCabe, Applied Dental Materials Ninth E

Termination
It is possible for the propagation reaction to continue until

the supply of monomer molecules is exhausted. In

practice however, other reactions, which may result in
the termination of a polymer chain. These reactions
produce dead polymer chains which are not capable of
further additions.
One example of termination is the combination of two
growing chains to form one dead chain as follows:
RO (M)n M + RO (M)x M RO (M)n M M
(M)x OR
Other examples of termination involve the reactions of

growing chains with molecules of initiator, dead polymer,

impurity or solvent, if present.

John F. McCabe, Applied Dental Materials Ninth E

Chemically Activated (Self-Cure)

Resins

Two pastes,
one of which contains the benzoyl peroxide initiator
the other an aromatic tertiary amine activator (e.g., N, N-

dimethyl-p-toluidine),
When the two pastes are mixed together, the amine reacts with the
benzoyl peroxide to form free radicals, and addition polymerization
is initiated.

PHILLIPS SCIENCE OF DENTAL MATERIALS 12TH E

 PROBLEMS:
1.

2.

3.

Almost impossible to avoid incorporating air into the

mix, thereby forming pores that weaken the structure
and trap oxygen, which inhibits polymerization during
curing.
No control over the working time after the two
components have been mixed. Therefore both insertion
and contouring must be completed quickly once the
resin components are mixed. Thus, today they are
mainly used for restorations and large foundation
structures (buildups) that are not readily cured with a
light source.
Formation of an oxygen inhibited layer. This reaction
forms an unpolymerized surface layer. The thickness of
the unpolymerized film on the surface is dependent on
PHILLIPS SCIENCE OF DENTAL MATERIALS 12TH E
the viscosity of the resin, the solubility of oxygen in the
monomer, and the initiating system used.

PHILLIPS SCIENCE OF DENTAL MATERIALS

Dual-Cured Resins
Able to overcome limits on curing depth and

some of the other problems associated with light.

Consist of two light-curable pastes
one containing benzoyl peroxide
one containing an aromatic tertiary amine

accelerator.
Cure slowly when mixed via the self-cure

mechanism. The cure is then accelerated on

command via light-curing promoted by the
amine/ photoinitiator combination.

PHILLIPS SCIENCE OF DENTAL MATERIALS 12

The major advantage of this system is assurance of

completion of cure throughout, even if photocure

is inadequate.
The disadvantages
porosity caused by the required mixing. But this has been

greatly alleviated by the use of mixing syringes.

Less color stability than with the photocure resins owing to
the aromatic amine accelerators, but this is still better
than for self-cure systems, since the concentration of the
accelerators is reduced compared with self-cure resins.
Intended for any situation that does not allow sufficient

light penetration to produce adequate monomer

conversionfor example, cementation of bulky ceramic
inlays.

PHILLIPS SCIENCE OF DENTAL MATERIALS 12

Polymerization shrinkage

Shrinkage can compromise marginal seal and rupture

adhesive bonds created at the tooth-restorative interface.

It has been claimed that the slight expansion, due to
absorption of water, over a period of several weeks following
placement can help to partially off-set the effects of
shrinkage.
Another potentially serious effect of shrinkage - stress
placed on tooth substance
particularly on the residual cusps of posterior teeth in relatively

large cavities. Such stresses, caused by the composite material

pulling-in cusps to which it may adhere, is thought to be
responsible for some cases of post-operative pain experienced
after placement of so-called posterior composites. In extreme
cases the stress on the tooth may be great enough to cause
cuspal fracture.

John F. McCabe, Applied Dental Materials Ninth E

PHILLIPS SCIENCE OF DENTAL MATERIALS 12

Craigs RESTORATIVE DENTAL

MATERIALS
THIRTEENTH EDITION

Reduction of Shrinkage Stresses

Two general approaches have been followed in

seeking to overcome the problem of stress

concentration and marginal failure experienced
with light-activated resins:
(1) reduction in volume contraction by altering the
chemistry and/or composition of the resin system
(2) clinical techniques designed to offset the effects
of polymerization shrinkage.
Incremental Buildup and Cavity Configuration
One technique attempts to reduce the C-factor,
which is related to the geometry of the cavity
preparation and represented by the ratio of bonded
to nonbonded surfacePHILLIPS
areasSCIENCE OF DENTAL MATERIALS 12

TH

PHILLIPS SCIENCE OF DENTAL MATERIALS 12

REFERENCES
John F. McCabe, Applied Dental

Materials Ninth Edition

PHILLIPS SCIENCE OF DENTAL MATERIALS
12TH Ed
Craigs RESTORATIVE DENTAL MATERIALS
THIRTEENTH EDITION