Journal of Oral Rehabilitation 2000 27; 488493

Degree of conversion in denture base materials for varied

polymerization techniques*
J. A. BARTOLONI*, D. F. MURCHISON , D. T. WOFFORD & N. K. SARKAR

*USAF Dental

Investigation Service, Brooks AFB, 59 Medical Wing/MRDG, Lackland AFB, TX, U.S.A., 374 Medical Group/SGD, Yokota AB, Japan and

Department of Biomaterials, Louisiana State University Medical Center, School of Dentistry, New Orleans, LA, U.S.A.

SUMMARY

New processing techniques for denture

base acrylic resins have been introduced which have
not comparatively quantified the residual monomer
content. While proper processing keeps the residual
monomer in a tolerable range for most patients,
tissue irritation and reaction due to potentially
higher residual monomer in these alternative techniques could be a clinical concern. Decreased degree
of conversion may influence physical properties as
well as biocompatibility. This investigation evaluated the residual monomer content of acrylic resins
cured by three different polymerization modes. Materials (polymerization system) evaluated were: Lu-

citone 199 (conventional process), Accelar 20

(rapid boil-out), and Acron MC (microwave).
Fourier transform infrared spectrometry (FTIR) was
employed to determine the degree of conversion. All
curing methods produced similar results (Lucitone
199 = 927% (021), Acron MC = 926% (057), Accelar 20 = 909% (073). Conversion for Accelar 20
(rapid boil-out technique), though statistically different (PB 005, ANOVA) from the other two materials
and polymerization techniques, was only slightly
less. It is unlikely that the rapid boil-out technique
would induce more adverse tissue responses than the
other techniques included in this study.

Introduction

mer free radicals. Flory (1969) describes the polymer

structure of poly (methyl methacrylate) as an asymmetric chain. Barron, Rueggeberg & Schuster (1992)
stated that the degree of monomer conversion of resin
materials is a measure of the carbon double bonds
(CC) converted into carbon single bonds (CC).
The goal of conventional/rapid curing of acrylic
resins is to completely polymerize the resin without
porosity. In the conventional/rapid curing methods,
the monomer molecules are moved by thermal shocks
from other molecules, and passively moved due to
external heat. During polymerization the monomer is
reduced. As temperature increases, molecular mobility
speeds up, leading to more complete polymerization. In
the microwave method, the monomer molecules are
moved by internal heat produced by a high-frequency
electro-magnetic field. With progressive polymerization of the monomer/polymer mix, the same amount
of energy is absorbed by less and less monomer. Poly-

Acrylic resins were first utilized as denture base materials in 1937 (Craig, 1993). Poly(methyl methacrylate) is
the primary base resin used today. Polymerization of
poly(methyl methacrylate) may be effected by heating
the polymer monomer mixture in a water bath, by
chemical activation at room temperature using a material such as dimethyl-p-toluidine, or by activating the
reaction using microwave energy or visible light
(Phillips, 1991).
Addition polymerization requires the activation of
the initiator (benzoyl peroxide) to provide free radicals.
Polymerization takes place as the free radicals open the
double bonds of the methyl methacrylate, creating a
chain reaction where the monomer attaches to poly* The opinions and assertions contained herein are the private
views of the authors and are not to be construed as the official
policy or position of the U.S. Government, the Department of
Defense, or the Department of the Air Force.
2000 Blackwell Science Ltd

488

POLYMERIZATION OF DENTURE BASE MATERIALS

merization of poly(methyl methacrylate), whether by
microwave or heat, may be affected by a variety of
time and temperature parameters, and varying
amounts of unreacted methyl methacrylate monomer
remain after the curing cycle. All acrylic resins contain
variable residual monomer levels depending on the
ambient conditions and the efficiency of heat transfer.
Flory (1969) characterizes the process as a combination
of effective monomer diffusion, exothermic heat, and
chain mobility to autoaccelerate the MMA conversion
to PMMA. Many investigations have demonstrated
that residual monomer content varied considerably
with curing conditions, and the amount of residual
monomer was one of the primary factors affecting the
properties of denture base materials produced under
different curing cycles (Smith 1958; McCabe & Basker,
1976; Austin & Basker, 1980, 1982; DeClerck, 1987; Al
Doori et al., 1988; Truong & Thomasz, 1988; Jerolimov
et al., 1989; Shlosberg, Goodacre & Munoz, 1989; Barron et al., 1992; Harrison & Huggett, 1992).
Residual monomer may diffuse from acrylic resin
resulting in irritation or allergic side effects (McCabe &
Basker, 1976; Schuster et al., 1995). For acrylic resins
to induce a primary irritation or sensitization, free
monomer must be leached out. There are well-documented reports of both hypersensitivity and local irritation caused by methyl methacrylate monomer
(McCabe & Basker, 1976; Austin & Basker, 1980;
Weaver & Goebel, 1980; Ali, Bates & Reynolds, 1986).
Proper processing techniques minimize residual
monomer content in denture bases and keep residual
monomer in the range of 1 3% which is well tolerated
by most individuals (Craig 1993).
Recently, Fourier transform infrared spectrometry
(FTIR) has become a popular tool for the analysis of
the extent of conversion in dental resins (Ferracane &
Greener, 1984). The literature is replete with conflict-

Table 1. Denture base materials examined

Materials

Manufacturer

Lucitone 199

Dentsply International
York, PA, U.S.A.
GC America, IL, U.S.A.

Acron MC
Accelar 20

Curing mode

Traditional heat-cure
(74 C, 9 h)
Microwave cure
(500 W, 3 min)
Miles, Inc. Dental Prod- Rapid boil-out (100 C,
ucts, South Bend, IN,
20 min)
U.S.A.

ing information regarding the varied residual monomer

content under different polymerization modes (Austin
& Basker, 1982; Huggett et al., 1984; DeClerck, 1987;
Al Doori et al., 1988; Truong & Thomasz, 1988;
Jerolimov et al., 1989; Harrison & Huggett, 1992;
Yunus, Harrison & Huggett, 1994). This investigation
used FTIR to compare the residual monomer levels for
three materials, each involving a different curing
method: Lucitone 199 (conventional long-cure), Accelar 20 (rapid cure), and Acron MC (microwave
cure).

Materials and methods

Three denture base resins, specifically formulated for
polymerization by different methods, were compared
under the processing conditions listed (Table 1). These
included a rapid-polymerized resin Accelar 20, a traditional heat-polymerized resin Lucitone 199, and a
microwave-polymerized resin Acron MC. Baseplate
wax, with dimensions of 50 50 1 mm was invested in the appropriate denture flasks. Three samples
of each resin-polymerization method were prepared
independently. The resins were processed by one operator according to the manufacturers recommendations
(Table 1). In this study, Lucitone 199 (conventional
heat-cured method) served as the control.
After deflasking, each specimen was prepared for
analysis with the FTIR spectrometer to determine the
degree of residual monomer content. The measurement of resin cure is established from the BeerLambert equation: A= abc, where A = absorbance;
a = molar absorptivity; b= path length, and c =concentration. Determining resin cure begins with calculating the aliphatic carbon-to-carbon double bonds
(CC) concentration of the uncured material at 1636
cm 1. The concentration of aliphatic CC is then determined from FTIR for a thin slice of cured material.
The degree of conversion (%) of monomer-to-polymer
is calculated by determining the proportion of remaining CC in the cured specimen in relationship to the
total CC available in the uncured state.
Loshaek & Fox (1953) developed a method to determine the degree of conversion of methacrylate-based

Miles Inc., Dental Products, South Bend, IN, U.S.A.

Dentsply International, York, PA, U.S.A.

GC America, Chicago, IL, U.S.A.

Shur Wax-hard, Miles Inc., Dental Products, South Bend, IN,

U.S.A.

2000 Blackwell Science Ltd, Journal of Oral Rehabilitation 27; 488 493

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490

J . A . B A R T O L O N I et al.
(Fig. 1). The IR spectra of the three monomers indicate
similar CC molar concentration, density, and WPMG.
A calibration graph was prepared relating absorption
peak height to the molar concentration of CC in the
undiluted solutions. Linear regression analysis was accomplished on the above data to generate the mathematical relationship between the two variables
enabling the determination of the CC concentration
from the absorption of the test monomer solution for
the three MMA monomers (Fig. 2).

Value of WPMG in uncured resin

Fig. 1. IR spectra of the three tested monomers.

resins having no internal standard (absorption of a

functional group that does not enter into reaction during curing), which was verified by Rueggeberg (1994).
This procedure is based upon the assumption that the
methacrylate group, as expressed by (CH2
C(CH3)CO) can be used as a gravimetric form of
concentration measurement. The absorbance value divided by the product of the path length and weight
percent methacrylate group (WPMG) can be considered a constant. Thus, the degree of monomer conversion may be expressed as a change in weight percent of
methacrylate groups remaining after polymerization as
compared to the amount present prior to curing.

Calibration graph for CC concentration

The three MMA monomers utilized were diluted with
spectrophotometric grade hexane. The number of
moles of CC per millilitre of each standard solution
was determined from the molecular weight and density. Each solution was analysed using a transmission
micro-liquid cell** with ZnSe windows at a path length
of 0025 mm. The spectra were compiled from 64 scans
at a resolution of 2 cm 1 on the FTIR. The absorption
peak height of the CC at 1636 cm 1 was calculated
** Model SL-3, International Crystal Labs, Garfield, NJ, U.S.A.

FTS-40, Bio-Rad, Digilab Division, Cambridge, MA, U.S.A.

The relationship demonstrated in Fig. 2 was used to

determine the undiluted CC molar concentration of
the three monomers from the IR. The weight of the
methacrylate groups in each millilitre of resin was
calculated by multiplying the molar concentration by
the molecular weight of a methacrylate unit (69081).
The WPMG was calculated by dividing the weight of
methacrylate groups in 1 mL resin by the density
(Table 2).

Specimen preparation for resin cure

Three specimens of each acrylic resin type were fabricated. The cured resin specimens were then ground
into thin films for FTIR analysis.

Resin cure with no internal standard

The height of the absorbance peak of the CC group at
1636 cm 1 was calculated for each of the three types
of cured acrylic resin specimens. The thickness of each
cured specimen was measured with a micrometer.
The remaining WPMG of each specimen was determined by:
Wr = A/T K,
where Wr = weight percent of remaining methacrylate
groups; A = height of CC absorbance peak height at
1636 cm 1; T= thickness of cured film (mm); and K=
optical constant for methacrylate group (064).
Resin cure was calculated by determining the proportion of WPMG available after curing (c) compared
to the amount present in the uncured (u) solution:

Model 106-101, Mitutoyo, MTI Corp., Paramus, NJ, U.S.A.

2000 Blackwell Science Ltd, Journal of Oral Rehabilitation 27; 488493

POLYMERIZATION OF DENTURE BASE MATERIALS

Fig. 2. Calibration curve

establishing the relationship
between IR absorbance peak height
and CC concentration.

Table 2. Weight percent of methacrylate groups in uncured monomers

Resins
Lucitone 199
Acron MC
Accelar 20

IR absorption
20543
20540
20522

No. of moles
CC/mL

Weight of methacrylate
groups/mL

Resin density
(g/mL)

Wt.% methacrylate
groups (WPMGu)

00094
00094
00094

06494
06494
06494

0945
0945
0945

6872
6872
6872

C = [1 WPMGc/WPMGu] 100%,
where C=percent monomer conversion; WPMGc =
weight percent methacrylate groups in cured resin; and
WPMGu = weight percent methacrylate groups in uncured resin.
Data were analysed via one-way ANOVA (a=005)
and when significant differences were discovered, a
Student Newman Keuls range test was employed.

Results
The linear regression analysis for the calibrated curve
of the dilutions of MMA yielded an excellent fit for the
three monomers (R 2 = 099). This demonstrated that
concentrations of unknown values of CC could reliably be determined by using their absorption peak
heights. The IR spectra for the three monomers indicated similar CC molar concentration, WPMG, and

density. The spectra overlap suggests that all three

materials are nearly identical in composition.
The results of the ANOVA for percentage of cure is
depicted in Table 3. The sample size employed and
observed effect size yielded a power of 0803 (a=
005). The degree of conversion of the rapid cure material (Accelar 20), was found to be statistically
significantly different (PB 005) than the rates of the
conventional long-cure and microwave materials.
However, the values of all materials exceeded a 90%
conversion, indicating a high degree of monomer conversion for all three methods.
Table 3. Analysis of variance for percent cure
Resins

WPMGc (s.d.)

% Cure (s.d.)

Lucitone 199*
Acron MC*
Accelar 20

50070 (0151)
50652 (0390)
61180 (0253)

9271 (0211)
9263 (0565)
9087 (0729)

N= 3; * denotes groups not statistically significant (P\005).

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J . A . B A R T O L O N I et al.

Discussion
Over the years, there has been a continual search for
improvements in processing acrylic resins. Two of the
more significant changes are improvements in working
properties of the dough moulding process and advancements in rapid curing cycles (Xia, Shi & He,
1996).
There are many variations of the curing cycle. The
conventional method is a long, slow-temperature curing cycle where the acrylic resin is processed for 9 h at
74 C, with no terminal boil. The rapid curing technique uses rapid heating in boiling water for 10
20 min. Specially formulated resins and pressurized
processes are required for rapid curing and attention to
detail in processing is critical. The main advantage for
the rapid curing technique is considerably reduced laboratory time. Austin & Basker (1982) stated that short
curing cycles ( B2 h) are more popular than long curing cycles ( \ 6 h).
This study showed that residual monomer did not
vary considerably under different curing conditions as
compared to findings by McCabe & Basker (1976). The
shorter curing cycles for Accelar 20 did not significantly affect the final degree of conversion. Previous
studies by Austin & Basker (1982), Huggett et al.
(1984), Al Doori et al. (1988), Jerolimov et al. (1989)
and Harrison & Huggett (1992), using different resins,
determined decreased conversion with this technique.
The microwave technique displayed similar mean rates
of conversion as compared to the conventional method
which differs from studies by DeClerck (1987) and
Truong & Thomasz (1988).
This investigation demonstrated that degree of conversion for these resins can be easily and accurately
calculated for acrylic resins without functional groups
acting as internal standards. Residual monomer content may be determined after calculating WPMG in
uncured specimens, curing the specimens, and measuring the thickness of cured samples and the aliphatic
CC absorption peak height.

Clinical implications
Denture base acrylic resins polymerized by the conventional, rapid boil, or microwave techniques all demonstrated similar residual monomer contents. Following
manufacturers recommendations, all the investigated

materials showed a consistent degree of conversion

(%) under the different curing conditions. Although
the rapid cure technique was found to be statistically
significantly different, owing to low sample standard
deviation, this curing method generally followed the
conversion rates of the conventional and microwave
methods. Clinically speaking, though other factors such
as strength, porosity, or fatigue resistance must be
considered in overall denture base performance, the
three curing techniques yielded conversion rates that
suggest potential success addressing leachable
monomer levels. Other authors (Lefebvre, Knoernschild & Schuster, 1994; Tsuchiya et al., 1994; Vallittu
et al., 1995) have suggested that soaking processed
denture prostheses in water prior to delivery may be
beneficial in reducing intraoral monomer release. Dental health care providers may feel confident in using
the tested techniques/materials in denture fabrication
depending on clinical needs and laboratory capabilities.

Conclusions
(1) This method of quantifying degree of polymerization represents a repeatable and expedient analysis of
monomer conversion without the use of an internal
standard.
(2) All curing methods obtained similar degrees of
conversion determined by FTIR.
(3) Conversion values for the rapid cure technique,
though statistically significantly lower in weight percent cure, were similar to the residual monomer levels
of the other polymerization techniques and would be
unlikely to induce a more adverse tissue response.

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Correspondence: Col Joseph A. Bartoloni, USAFSAM/AED, 2509

Kennedy Circle, Bldg 125 Rm 215, Brooks AFB, TX 78235-5117,
U.S.A. E-mail: joseph.bartoloni@brooks.af.mil

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