Review Article
Living Polymerization Techniques and Their Utility in Material Synthesis
Diogo de Azevedo Miranda1* and Anderson Catelan2
1Doctor of the Dentistry Program of SUPREMA/JF, Hospital e Maternidade Therezinha de Jesus, Brazil
2Department of Restorative Dentistry, Piracicaba Dental School, University of Campinas, Brazil
*Corresponding author: Diogo de Azevedo Miranda, Doctor of the Dentistry Program of SUPREMA/JF and Hospital e Maternidade Therezinha de Jesus (HMTJ)), Brasil, Alameda Salvaterra 200, 36033-003, Juiz de Fora, MG, Brazil
Published: 26 Jan, 2018
Cite this article as: de Azevedo Miranda D, Catelan A.
Living Polymerization Techniques and
Their Utility in Material Synthesis. Ann
Clin Case Rep. 2018; 3: 1494.
Abstract
The polymeric materials are used in several applications. An adequate polymerization of these materials is fundamental to improve the physical and chemical properties. The aim of this study was related some findings of role of polymerization techniques on the behavior of resin-based materials.
Introduction
The polymer-based materials have been used in several applications. In contemporary
dentistry these materials are frequently used and light curing is commonly required during clinical
procedures. The professionals daily performed the polymerization of monomers into polymers as a
simple process, but several implications are present in this reaction.
Initiator
In the late 1940s the use of acrylic resin for esthetic restorations was usual. However, with
development of Bis-GMA by Bowen in the early 1960s, the resin-based materials were rapidly
applied in the dental restorations [1].
The first composites resins were self-cured, paste-paste system; these materials used the benzoyl
peroxide as initiator of the polymerization reaction [2]. In 1970 the light-activated composites were introduced, maximizing working time and minimizing setting time [3], and camphorquinone (CQ) has been the photoinitiator more used [2,4]. Recently, due to the greater demand for esthetic treatments the search for bleaching procedure has increased, but the restorations of bleached teeth with CQ-based dental composites is compromised in most cases, because this photoinitiator is
yellowish, thus others initiators have been used, such as 2,4,6-trimethylbenzoyl-diphenylphosphine
oxide and bis(2,3,6-trimethylbenzoyl)-phenylphosphineoxide [4].
Polymerization reaction
The most contemporary dental materials are light-activated and use the popular basic
formulation composed by a visible light-curing photoinitiation system composition (generally CQ)
and a tertiary amine co-initiator introduced to many years and, which remains in use today [4]. The polymerization reaction occurs when the initiator molecule absorbs a photon of light (for
CQ approximately 470 nm wavelength) [5], an electron of this molecule is boosted to a higher level of energy, leaving it a triplet state excitation [6]. Thus, the photoinitiator collides with tertiary amine, and the free radicals amino and ketyl are formed. This amino radical can react with a carbon double bond (C=C) in the aliphatic group of the monomer chains, initiating the polymerization reaction, in
which monomers that have a C=C bond broken in one or the two ends react with other monomers
in the same situation forming polymer structure [4,7].
Light-curing units
The first Light-Curing Unit (LCU) emitted ultraviolet radiation through a quartz rod from a
high-pressure mercury source [4]. However, this device showed some deficiencies, such as ability
of the light to penetrate within material limited in depth, potential for harmful effects of the short
wavelength energy being exposed to human eyes, and changes in the oral microflora [4,8,9]. In an attempt to solve some these problems was developed the LCU that emits visible radiation. The
device consists of a quartz-tungsten-halogen (QTH) lamp and a bandpass filter, which allows
pass only light between 400 to 550 nm of wavelengths [4]. QTH unit has been used for a long time, but bulb overheating results in light power reduction over time due to the lamp and filter
degradation [10]. The laser unit was initially in dentistry to improve vital dental bleaching efficacy [11]. Posteriorly it was use to cure light-activated materials, obtaining
adequate physical properties of restorative materials [12]. However,
this device has elevated cost and only clinician could operate the
unit, besides some researchers relate that individual energy delivery
for optimal performance is necessary for each brand and shade of
composite [4,13].
Plasma-arc curing (PAC) source was imported from Europe due
to dental auxiliary personnel was prohibited to use the laser in USA.
A high light emission is created by the electrical current generates
between two electrodes separated by a small distance in a highpressure
ionized gas chamber [4,14]. The first devices required filter
because infrared light and ultraviolet is generated, but later this units
were adapted in visible light wavelength. The light output is extremely
high (~2000 mW/cm2) and materials can be photopolymerized with
short time, but rapid polymerization can compromise the marginal
adaptation of restorations and PAC units are expansive [1,14]. The
light-emitting diode (LED) technology was introduced more recently
for use in dentistry and considered a light source efficient and costeffective.
Theses units have peak wavelength near from maximum
absorption of CQ, lower degradation, and no filter is necessary, due
to emission of blue light spectrum [4,10]. The first generation LED
was introduced at the end of 2000, however it had a typical design of
an assemblage of multiple LED elements (5 mm lamp, individual),
array from 7 to 64 were available, resulting in low luminance difficult
the competition with standard QTH unit [4].
Advances in LED industry technology allowed changing multiple
emitting lamps for a single chip, with similar luminance as 10-
20 individual 5 mm lamp of the 1st generation. Thus, the second
generation LED increased the irradiance, but a similar wavelength
range persisted and inabilities to light cure others initiators non-CQ
continued in this generation [4].
Despite of the highest light power of 2nd generation LED, the
cure of materials using others photoinitiators is compromised. Thus,
in third generation LED the manufacturers incorporated different
wavelengths chips, which permit effective curing for not only CQ
initiator and sufficient irradiance [4].
Light-curing protocols
In the conventional curing protocol a constant irradiance is
used along the polymerization of light-activated materials. However,
these materials show post-gel shrinkage and some curing methods
were developed [15,16]:(1) pulse delay polymerization consists in
a short flash of light initially followed by a waiting time of several
minutes before of the final cure; (2) soft-start curing method uses a
pre-polymerization at low-intensity light followed by a final cure at
high intensity; and (3) in the ramp mode a gradual increase of light
power is performed during the polymerization time. Some LCUs
has this curing mode pre-programed or it can be carried out with
conventional device by the increase of distance between the light
guide tip from material irradiated, thus the approximation of the tip
gradually increase the irradiance.
These alternative light-curing protocols aimed to increase
pre-gel phase of resin-based materials by the slow cure, to reduce
polymerization contraction due to stress relief, and final time of
cure with high light power, to obtain adequate C=C conversion
rate. However, it is reported that slow cure promotes few centers of
polymer growth, which will result in a more linear polymer structure
with relatively few crosslinks, more susceptible to degradation to food
substances and enzymatic attack.
On the other hand, it is related that rapid cure results in a
multitude of growth centers, and consequently a polymer with higher
crosslink density content [17]. However, the fast cure increases the
viscosity of the system and reduces the molecular mobility, which
promotes auto-deceleration of the polymerization reaction [18]. Thus,
LCUs with irradiance extremely low and high is not recommended to
reach adequate conversion rate and formation of a polymer structure
with physical properties.
Problems related to polymerization reaction
An inherent problem of resinous materials is the polymerization
shrinkage, which range from 2 to 5 vol% [19]. Furthermore, a
significant proportion of unreacted monomer due the incomplete
conversion of monomer into polymer is reported [17].
However, the increase on monomer conversion promotes
higher shrinkage strain and, consequently, resultant stress at toothrestoration
interface, increasing the likelihood of mechanical failure,
which it permits the ingress of bacteria causing pulpal irritation. In
addition, stress may results in cuspal deflection, enamel microcrack
propagation, and enamel fracture [19].
Different incremental composite placement techniques [20],
light-curing protocols, and intermediate layer with hybrid glass
ionomer or flowable composite [21] were proposed in the attempt to
decrease the shrinkage stress effects and, consequently, resulting in
lower clinical failure rate of resin-based restorations.
Constant researches with modification on the formulations
of organic matrix chemistry have been performed to reduce
polymerization shrinkage; such as silorane monomer developed from
the reaction of the oxirane and siloxane molecules [19], dimer-acid
chemistry derived monomers [22], resin contains a polymerization
modulator [23], and others.
Silorane is a new monomer system, its polymerization occurs by a
cationic reaction by the ring opening of oxirane moiety instead of free
radical cure of conventional methacrylate composite resins, resulting
on the lower contraction [24]. Others methacrylate-based composites
decreased the shrinkage by modification on the monomer matrix,
as introduction of dimer acid dimethacrylate monomers as diluent
co-monomers [22] and chemical incorporation of a polymerization
modulator in the center of the light curable resin backbone [22].
Conclusion
The polymerization reaction is directly related to improve the physical and chemical properties of curable materials. Therefore, an adequate conversion rate is strongly influenced by polymerization technique used and fundamental to clinical success of resinous materials longevity.
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