ACRYLIC DENTAL RESIN

As previously mentioned, for a sythetic resin to be useful in dentistry, it must

exhibit exceptional qualities regarding its chemical and dimensional stability and
yet it must also possess properties that render it relatively easy to process. It
must be strong and hard, but not brittle. A few acrylic resins used in dentistry are
discussed in the following.
ACRYLIC RESINS
The acrylic resins are derivatives of ethylene and contain a vinyl ( C=C
group in their structural formula:
There are at least two acrylic resin series that are of dental interest. One series is
derived from acrylic acid, CH2 C HCOOH , and the other from methacrylic acid,
CH2 C ( CH 3 ) COOH . Both of these compounds polimerize by addition in the
usual manner. Although the poliacids are hard and transparent, their polarity,
relate to the carboxyl group, cause a general softenig and loss of strength. For
example, if R represents any ester raical, the polimerization reaction for
poly(methacrylate) will be:

Because R can be almost any organic or inorganic radical, it is evident that

thousands of diferent acrylic rsins are capable of formation. Such a consideration
does not include the possibilities of copolimerization, which are even greater.
The effect of esterification on the softening point of a few of the
poly(methacrylate) compound is shown in table 7-1.
For short chain legths, increasing the length of the side chain lowers the
softening point or glass transition tmperature. For example, poly(methyl
methacrylate) is the hardest resin of the series with the higest softening
temperature. Poly(ethylpropy methacrylate) has an even lowers softening point
and hardness.
Methyl Methacrylate
Poly(methyl methacrylate) by itself is not used i dentistry to great extent in
molding procedures. Rather, the liquid monomer methyl methacrylate (Fig. 7-15)
is mixed with the polymer, which is supplied in the powdered form. The monomer
partially dissolves the polymer to form a plastic dough. This dough is packed into
the mold, and the monomer is polymerized by one of the method discussed
previuously. Consequently, the monomer methyl methacrylate is of considerable
importance in dentistry.
Methyl methacrylate is a transparent liquid at room temperature with the
folowing physical properties:

Molecular weight = 100

Melting point = -480 C
Boiling point = 100.80C (note how close this is to the boiling point of
water)
Density = 0.945 g/mL at 200C
Heat of polymerization = 12.9 kcal/mol
Methyl methacrylate exhibits a high vapor pressure and is an excellent
organic solvent. Although the polymerization of methyl methacrylate can
be nitiated by visible light, ultraviolet light, or heat, it is commonly
polymerized in dentistry by the use of a chemical initiator, as described
previously.
The conditions for the polymerization of methyl methacrylate are not
critical, provided that the reaction is not carried out too rapidly. The
degree of polymerization varies with the conditions of polymerization,
such as the temperature, method of factors. Because they polymerize
readily under the conditions of use, the methacrylate monomers are
particularly useful in dentistry. Many other rsin systms do not polymerize
at room temperature in the presence of air. A volume shrinkage of 21%
occurs during the polimerization of the pure methyl methacrylate
monomer.
Poly(methyl Methacrylate)
Poly(methyl methacrylate) (see Fig. 7-15) is a transparent resin of
remarcable clarity; it transmts light in the ultraviolet range to a
wavelength of 250 nm. It is hard resin with a knoop hardness number of
18 to 20. It has a tensile strength approximately 60 MPa, a density of 1.19
g/cm3, and a modulus of elasticity of approximately 2.4 Gpa (2400 Mpa).
This polymer is extremely stable. It does not discolor in ultraviolet light,
and it exhibits remarkable aging properties. It is chemically stable to heat
and softens at 1250C, and it can be molded as a thermplastic material.
Between 1250 and 2000C, depolymerization takes place. At approximatelly
4500C, 90% of the polymer depolymerizes to form the monomer.
Poly(methyl methacrylate) of high molecular weight degrades to a lowers
polymer at the same time that it converts t the monomer.
Like all acrylic resins, poly(methyl methacrylate) exhibits a tendency to
absorb water by a process of imbbition. Its noncrystalline structure
possesses a high internal eneregy is required. Furthermore, the polar
carboxyl group even though esterified, can form a hydrogen bridge to a
limited extent with water. Because poly(methyl methacrylate) is a linear
polymer, it is soluble in a number of organic solvents that may be found in
a dental laboratoy or operatory, such as chloroform and acetone.
Multifunctional Methacrylate and Acrylate Resins

The backbone of molecule formed in this sytem can have any shape, but
methacrylate groups are foud at the ends of the chain or at the end of branching
chains. One of the first multifunctional methacrylates used in dentistry was
bowens resins, or bis-GMA (Fig.7-16). The bis-GMA resin can be described as an
aromatic ester of a dimethacrylate, synthesized from an epoxy resin (ethylene

glycol of bis-phenol A) and methyl methacrylate. Because bis-GMA has two

OH

groups that form hydrogen bonds between the monmers, it is extremely

viscous. A low viscousity dimethacrylate, such as triethyleneglycol

dimethacrylate (TEGDMA), is blende with it to reduce viscosity (Fig. 7-17).
The rigid central core of two aromatic groups reduces the ability of bis-GMA
molecules to rotate during polimerization process. Therefore, one of the
methacrylate groups reacts often, where as the other does not. This proces
results in a bi-GMA molecule that forms a branch, or pendant grou, along the
polymer chain. Some of these branches cross-link with adjacent chains, and
some do not. To quantify the ratio, R, of unreactedmethacrylate groups before
and after polymerization. The degree of conversion, expressed in percentage of
consumed methyl methacrylate groups, can be determined from formula:
(1-R)x 100= degree of conversion
Various dimethacrylate resin combinations have been explored through the years
in attempts to reduce viscosity and to increase the degree of conversion. One
resin group that has shown promise is urethane dimethacrylate (UDMA). This
UDMA group can be described as any monomer chain containing one or more
urethane groups and two methacrylate end groups (Fig. 7-18).
In addition to the dimethacrylatesmentioned previously, other multifunctional
resins have been introduced to dentistry during the last few years. For example,
in some dentin bonding agents a monomer called dipentaerythiol penta-acrylate
monophosphate (PENTA-P) is used (Fig.7-19). As seen from the PENTA-P formula,
this monomer contains as many as five acrylate groups per monomer molecule.
Another multifunctional resin that has been used extensively during the last few
year is poly(acrilic acid), to which hydroxyethyl methacrylate (HEMA) has been
grafted (Fig. 7-20). Such a modified poly(acrylic acid) (PAA) is used in lightcurable glass ionomer cements (see Chapter 16). During light exposure, free
radical polymerization is initiated, causing the methacrylate groups to react. The
reaction that cross-link the PAA molecules costitutes the initial setting reaction.
After this reaction, the carboxylate groups continue to react with the glass
particles through an acid-base reaction. During this reaction, the PAA releases
the hydrogen ions and the PAA chains become negatively charged (see Fig.16-11
and Fig. 16-17).
These negatives charges, however, are balanced by cations leached from the
glass. These cations, such as Ca2+ and Al3+, form ionic bonds between the chains
that now also become ionically cross-linked. In addition, the negatively charged
PAA chains also form bonds to tooth tissues containing cations such as Ca 2+.