Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins

Abstract

Objectives

The purpose of this study was to evaluate the reactivity and polymerization kinetics behavior of a model dental adhesive resin with water-soluble initiator systems.

Methods

A monomer blend based on Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin, which was polymerized using a thioxanthone type (QTX) as a photoinitiator. Binary and ternary photoinitiator systems were formulated using 1 mol% of each initiator. The co-initiators used in this study were ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thiobarbituric acid (BARB), p -toluenesulfinic acid and sodium salt hydrate (SULF). Absorption spectra of the initiators were measured using a UV–Vis spectrophotometer, and the photon absorption energy (PAE) was calculated. The binary system camphorquinone (CQ)/amine was used as a reference group (control). Twelve groups were tested in triplicate. Fourier-transform infrared spectroscopy (FTIR) was used to investigate the polymerization reaction during the photoactivation period to obtain the degree of conversion (DC) and maximum polymerization rate ( R p max ) profile of the model resin.

Results

In the analyzed absorption profiles, the absorption spectrum of QTX is almost entirely localized in the UV region, whereas that of CQ is in the visible range. With respect to binary systems, CQ + EDAB exhibited higher DC and <SPAN role=presentation tabIndex=0 id=MathJax-Element-1-Frame class=MathJax style="POSITION: relative" data-mathml='Rpmax’>RmaxpRpmax
R p max
values. In formulations that contained ternary initiator systems, the group CQ + QTX + EDAB was the only one of the investigated experimental groups that exhibited an <SPAN role=presentation tabIndex=0 id=MathJax-Element-2-Frame class=MathJax style="POSITION: relative" data-mathml='Rpmax’>RmaxpRpmax
R p max
value greater than that of CQ + EDAB. The groups QTX + EDAB + DPIHFP and QTX + DPIHFP + SULF exhibited values similar to those of CQ + EDAB with respect to the final DC; however, they also exhibited lower reactivity.

Significance

Water-soluble initiator systems should be considered as alternatives to the widely used CQ/amine system in dentin adhesive formulations.

Introduction

Dental adhesive system formulations fundamentally contain resin monomers, polymerization initiators, inhibitors or stabilizers, solvents and sometimes inorganic fillers . According to their chemical structures, these components may exhibit hydrophobic or hydrophilic behavior .

The hydrophilic components, such as 2-hydroxyethylmethacrylate (HEMA), are required to increase monomer infiltration into wet and demineralized dentin . However, the hydrophobic components used in these materials, such as bisphenol A glycidyldimethacrylate (Bis-GMA), are known to be responsible for enhancing the mechanical properties of the formulation and its compatibility with restorative composites or resin cements .

Resin monomer infiltration into the spaces around exposed collagen fibrils depends on the results of dentin demineralization before hybrid layer formation . This interface must exhibit bond strength values that are sufficiently high to counteract the stresses generated by polymerization shrinkage and mastication and to maintain these values over time, which is a critical factor for restoration durability. However, in vivo and in vitro studies have shown that the durability of the bond continues to be a problem . The main factors that explain the reduced longevity of bonded interfaces include incomplete impregnation of collagen fibrils by the monomer, high permeability of the bonded interfaces, sub-polymerized polymers, phase separation and activation of collagenolytic enzymes .

Phase separation of Bis-GMA-based adhesives has been shown to occur in the presence of water . Consequently, limited conversion from monomers into a rigid polymer network occurs when hydrophobic molecules are surrounded by a hydrophilic matrix, usually HEMA. This important outcome suggests that the traditional photo-initiator molecules either become isolated within the hydrophobic phase or that they are incompatible with hydrophilic HEMA .

The main photoinitiator system used in commercially available dental adhesive systems is based on the visible-light photosensitizer camphorquinone (CQ) . In view of the phenomenon of phase separation that occurs in these materials and its consequences in terms of longevity and biocompatibility, the development of a more efficient adhesive photoinitiator system is necessary. A water-soluble photoinitiator system appears to be an interesting alternative to increase monomer/polymer conversion in Bis-GMA/HEMA-based adhesives. Some ionic derivatives of thioxanthone dyes are water miscible and therefore may represent an interesting alternative for the polymerization of dental adhesives . In addition, iodonium salts seem to be efficient water-soluble co-initiator systems that improve the polymerization rate of dental monomers when camphorquinone is used, even in the presence of a solvent .

Organic-acid derivatives can also be used to play the role of water-soluble co-initiators for this type of material, and sulfinic acid derivatives and barbituric acid have both already been used for the polymerization of dental materials.

Although recent studies have proved that the polymerization behavior of dental monomers is beneficial when the aforementioned components are used, little information exists about the efficiency of an iodonium salt or organic acid derivative as co-initiators for a thioxanthone derivative, and this question needs clarification. Consequently, the aim of this study was to evaluate the behavior of a model dental adhesive resin, in terms of its reactivity and polymerization kinetics, when a water-soluble initiator system is added to its formulation. Importantly, in addition exhibiting water solubility, the photoinitiator system might exhibit high polymerization reactivity when used in dental adhesives. The hypotheses tested were that: (1) the combination of QTX + an iodonium salt and/or organic acid derivatives is able to promote satisfactory polymerization and (2) the addition of QTX, an iodonium salt or organic acid derivatives may improve the polymerization efficiency of a CQ-based model dental adhesive resin.

Materials and methods

Reagents

Bisphenol A glycidyldimethacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), 2-hydroxyethyl methacrylate (HEMA) and camphorquinone (CQ) were supplied by Esstech (Essignton, PA, USA). Ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thio-barbituric acid (BARB), p -toluenesulfinic acid sodium salt hydrate (SULF) were purchased from Aldrich Chemical (Milwaukee, WI, USA), and the 2-hydroxy-3-(3,4 dimethyl-9-oxo-9 H -thioxanthen-2-yloxy)- N , N , N -trimethyl-1-propanaminium chloride (QTX) was obtained from Nippon Ink (Japan). All reagents were used as received without further purification. Characteristics of the initiators used in this study are shown in Table 1 .

To perform the monomer photoactivation, a halogen light-activation unit (XL 3000, 3M ESPE, St. Paul, MN, USA) was used and the irradiation value (450 mW/cm 2 ) was determined with a handheld radiometer ( model 100 ; Demetron Kerr, Orange, CA, USA).

Formulations

A model dental adhesive resin was formulated by intensive mixing of 50 wt.% Bis-GMA, 25 wt.% TEGDMA and 25 wt.% HEMA. Unitary, binary and ternary systems were evaluated, totaling 12 experimental groups. Each initiator was added at 1 mol% for all groups relative to number of moles of monomer. No radical scavenger was added to avoid interference in the polymerization kinetics.

Absorption spectrophotometric analysis

The initiators were used as received and solvent used was 2-hydroxyethyl methacrylate (HEMA). Absorption spectra were determined in the 300–550 nm range using a UV–Vis spectrophotometer (U-2000, Hitachi High-Technologies, Japan). The spectra were collected using a quartz cell with a path length of 1.0 cm. Absorption spectra were recorded for each photo and co-initiator ( Fig. 1 ).

Fig. 1
Absorption spectra of the initiators (a–e) and the emission spectra of the LCU (f).

Emission spectrophotometric analysis

Emission spectra of the light-curing unit XL 3000 was determined in the 360–560 nm range using a laboratory radiometer (Spectrometer 100, Labsphere, Sutton, NH, USA) connected to an integrating sphere (LabSphere 2000, LabSphere, Sutton, NH, USA). The values were presented as spectral readings ( Fig. 1 F), in which the area under the curve was integrated to obtain the total power output between 360 and 560 nm. The spectrometer was calibrated using a National Institute of Standards and Technology (NIST, Gaithersburg, MD) light source.

Kinetics of polymerization evaluated by RT-FTIR spectroscopy

The degree of conversion of the experimental materials was evaluated using Fourier-transform infrared spectroscopy with a spectrometer (Prestige 21, Shimadzu, Japan) equipped with an attenuated total reflectance device. The reflectance device was composed of a horizontal ZnSe crystal with a 45° mirror angle (PIKE Technologies, Madison, WI, USA). A support was coupled to the spectrometer, which was used to fix the light-curing unit in place and standardize the distance at 5 mm in a parallel position between the fiber tip and the sample. The IRSolution software package (Shimadzu, Columbia, MD, USA) was used in the monitoring scan mode using Happ–Genzel appodization in the range of 1750–1550 cm −1 , a resolution of 8 cm −1 and a mirror speed of 2.8 mm/s. With this configuration, one scan was acquired every 1 s during photoactivation.

Analysis was performed at a controlled room temperature of 23 °C (±2 °C) and 60% (±5%) relative humidity. The sample (3 μL) was directly dispensed onto the ZnSe crystal and was light-activated for 30 s. The degree of conversion was calculated as described previously based on the intensity of the carbon–carbon double-bond stretching vibrations (peak height) at 1635 cm −1 and using the symmetric ring stretching at 1610 cm −1 from the polymerized and non-polymerized samples as an internal standard. Analyses were performed in triplicate ( n = 3). Data were plotted and curve fitting was applied using logistic non-linear regression. In addition, the polymerization rate ( R p (s −1 )) was calculated as the degree of conversion at time t subtracted from the degree of conversion at time t − 1. The coefficient of determination was greater than 0.98 for all curves.

Materials and methods

Reagents

Bisphenol A glycidyldimethacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), 2-hydroxyethyl methacrylate (HEMA) and camphorquinone (CQ) were supplied by Esstech (Essignton, PA, USA). Ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thio-barbituric acid (BARB), p -toluenesulfinic acid sodium salt hydrate (SULF) were purchased from Aldrich Chemical (Milwaukee, WI, USA), and the 2-hydroxy-3-(3,4 dimethyl-9-oxo-9 H -thioxanthen-2-yloxy)- N , N , N -trimethyl-1-propanaminium chloride (QTX) was obtained from Nippon Ink (Japan). All reagents were used as received without further purification. Characteristics of the initiators used in this study are shown in Table 1 .

To perform the monomer photoactivation, a halogen light-activation unit (XL 3000, 3M ESPE, St. Paul, MN, USA) was used and the irradiation value (450 mW/cm 2 ) was determined with a handheld radiometer ( model 100 ; Demetron Kerr, Orange, CA, USA).

Formulations

A model dental adhesive resin was formulated by intensive mixing of 50 wt.% Bis-GMA, 25 wt.% TEGDMA and 25 wt.% HEMA. Unitary, binary and ternary systems were evaluated, totaling 12 experimental groups. Each initiator was added at 1 mol% for all groups relative to number of moles of monomer. No radical scavenger was added to avoid interference in the polymerization kinetics.

Absorption spectrophotometric analysis

The initiators were used as received and solvent used was 2-hydroxyethyl methacrylate (HEMA). Absorption spectra were determined in the 300–550 nm range using a UV–Vis spectrophotometer (U-2000, Hitachi High-Technologies, Japan). The spectra were collected using a quartz cell with a path length of 1.0 cm. Absorption spectra were recorded for each photo and co-initiator ( Fig. 1 ).

Fig. 1
Absorption spectra of the initiators (a–e) and the emission spectra of the LCU (f).

Emission spectrophotometric analysis

Emission spectra of the light-curing unit XL 3000 was determined in the 360–560 nm range using a laboratory radiometer (Spectrometer 100, Labsphere, Sutton, NH, USA) connected to an integrating sphere (LabSphere 2000, LabSphere, Sutton, NH, USA). The values were presented as spectral readings ( Fig. 1 F), in which the area under the curve was integrated to obtain the total power output between 360 and 560 nm. The spectrometer was calibrated using a National Institute of Standards and Technology (NIST, Gaithersburg, MD) light source.

Kinetics of polymerization evaluated by RT-FTIR spectroscopy

The degree of conversion of the experimental materials was evaluated using Fourier-transform infrared spectroscopy with a spectrometer (Prestige 21, Shimadzu, Japan) equipped with an attenuated total reflectance device. The reflectance device was composed of a horizontal ZnSe crystal with a 45° mirror angle (PIKE Technologies, Madison, WI, USA). A support was coupled to the spectrometer, which was used to fix the light-curing unit in place and standardize the distance at 5 mm in a parallel position between the fiber tip and the sample. The IRSolution software package (Shimadzu, Columbia, MD, USA) was used in the monitoring scan mode using Happ–Genzel appodization in the range of 1750–1550 cm −1 , a resolution of 8 cm −1 and a mirror speed of 2.8 mm/s. With this configuration, one scan was acquired every 1 s during photoactivation.

Analysis was performed at a controlled room temperature of 23 °C (±2 °C) and 60% (±5%) relative humidity. The sample (3 μL) was directly dispensed onto the ZnSe crystal and was light-activated for 30 s. The degree of conversion was calculated as described previously based on the intensity of the carbon–carbon double-bond stretching vibrations (peak height) at 1635 cm −1 and using the symmetric ring stretching at 1610 cm −1 from the polymerized and non-polymerized samples as an internal standard. Analyses were performed in triplicate ( n = 3). Data were plotted and curve fitting was applied using logistic non-linear regression. In addition, the polymerization rate ( R p (s −1 )) was calculated as the degree of conversion at time t subtracted from the degree of conversion at time t − 1. The coefficient of determination was greater than 0.98 for all curves.

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Nov 28, 2017 | Posted by in Dental Materials | Comments Off on Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins
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