Development of new diacrylate monomers as substitutes for Bis-GMA and UDMA

ObjectiveBisphenol A-glycidyl methacrylate (Bis-GMA) and urethane dimethacrylate (UDMA) are widely used as the primary components of (meth)acrylic monomers. However, the use of Bis-GMA, which is a bisphenol A derivative, in dentistry is being questioned after bisphenol A was found to exhibit estrogenic activity. Although UDMA is being considered as a substitute for bis-GMA, the mechanical properties of cured resin composites containing UDMA are less than desirable. Therefore, in this study, we developed new alternative (meth)acrylic monomers to enhance the mechanical strength of cured composite resins.MethodsFive urethane acrylic monomers were synthesized in this study as (meth)acrylic monomer substituents to replace Bis-GMA and UDMA. The elastic modulus, strength, and breaking energy values of cured resins consisting of mixtures of the urethane acrylates and diluting monomers were determined using the three-point flexural test. The data obtained were analyzed using one-way ANOVA and the post-hoc Tukey HSD tests (p < 0.05). Viscosities of the urethane acrylic monomers were measured with a cone-plate viscometer. Refractive indices of the urethane acrylic monomers were determined with an Abbe refractometer.ResultsThe results of the three-point flexural tests revealed that the cured urethane acrylic monomer-based resin exhibited higher elastic modulus (up to 40%) and strength (up to 21%) compared to the cured UDMA-based resin. Viscosity and refractive index of the urethane acrylic monomers were between those of UDMA and Bis-GMA.SignificanceThe developed urethane diacrylates prepared from diisocyanates which have an aromatic or aliphatic ring, 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI), or norbornane diisocyanate (NBDI) are worth considering as alternative options of Bis-GMA and UDMA for restorative resin composites.     

Physical properties of light-cured opaque resin. (1) Influence of monomer composition

Light-cured opaque resins with excellent physical properties were prepared using five types of monomer liquid and titanium dioxide as the powder. The five opaque resin monomer liquid had the following monomer compositions. Methyl methacrylate (MMA)/di(methacryloxyethyl) trimethylhexamethylene diurethane (UDMA) = 70/30 (M-U), MMA/neopenthylglycol dimethacrylate (NPG)/UDMA = 45/45/10 (M-N-U), UDMA/MMA = 70/30 (U-M), 2,2-bis (4-methacryloxypolyethoxy phenyl) propane (2.6 E)/2,2-bis [4-(3-methacryloxy-2-hydroxy propoxy) phenyl] propane (Bis-GMA)/triethyleneglycol dimethacrylate (3 G) = 60/35/5(2.6-B-3) and 3 G/UDMA = 70/30 (3-U) by weight. The bond strength, photo-curability and handling properties of the opaque resin were improved. Three MMA-based opaque resins showed nearly the same values in Knoop hardness number, diametral tensile strength and shear bond strength. The depth of cure increased with the decrease in MMA content of monomer composition, while the amount of residual monomer decreased. The 2.6-B-3 opaque resin had nearly the same properties in depth of cure and Knoop hardness number as the 3-U opaque resin. However, the 2.6-B-3 and 3-U opaque resins had a diametral tensile strength more than twice as high as that of the U-M opaque resin. The bond strength of three MMA-based opaque resins showed 0MPa after 5,000 thermocycles, while the 2.6-B-3 opaque resin, about 16 MPa, and the 3-U opaque resin, about 25 MPa. Therefore, the bond strength of the opaque resin was influenced by monomer composition. 3G-UDMA opaque resin showed excellent physical properties and may be clinically acceptable to bond fixed prosthodontic composite.     

Network structure of Bis-GMA- and UDMA-based resin systems

OBJECTIVES: The commonly used dental base monomers 2,2-bis[p-(2'-hydroxy-3'-methacryloxypropoxy)phenylene]propane (Bis-GMA) and 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane (UDMA) require the use of a diluent monomer, such as triethylene glycol dimethacrylate (TEGDMA). The aim of this study was to measure double bond conversion of UDMA/TEGDMA and Bis-GMA/TEGDMA polymeric systems, determine the leachable portion, and analyze network formation by evaluating crosslinking and pendant double bonds. METHODS: UDMA or Bis-GMA was combined with TEGDMA in systematic increments and irradiated to form light cured polymers. Fourier transform infrared spectroscopy in the near-infrared region was used to measure double bond conversion. The leachable sol fraction was analyzed by 1H NMR. Resin composites were formulated. Flexural strength was measured by three-point bending and volumetric shrinkage was determined with a mercury dilatometer. RESULTS: The amount of base monomer greatly influenced double bond conversion, sol fraction, and crosslinking. Increasing base monomer concentration decreased double bond conversion, increased the leachable fraction, and decreased crosslinking and network formation. At mole fractions higher than 0.125, the UDMA polymers had significantly higher conversion than the Bis-GMA polymers. Bis-GMA polymers had higher leachable amounts of unreacted monomer, while UDMA mixtures had more crosslinking than the Bis-GMA mixtures. In regards to the physical properties of resin composites, increasing the base monomer improved flexural strength and decreased volumetric shrinkage. SIGNIFICANCE: This systematic study for the evaluation of conversion, leachability, crosslinking, and network structure along with physical properties, like volumetric shrinkage and flexural strength, are required for the optimization of competing desirable properties for the development of durable materials.     

The application of fluorinated aromatic dimethacrylates and diacrylates to light-cured composite resins. 1. Improvement of transmittance of composite

To improve the transmittance of light-cured composite resins, the matching of the refractive indices of the matrix monomer and filler were examined. Eight fluorinated aromatic dimethacrylates and diacrylates with a low refractive index were synthesized. Three of these monomers had a poor solubility to TEGDMA. The depths of cure and the other physical properties of eight experimental composites prepared from one of five fluorinated monomers, TEGDMA and UDMA were determined compared with those of the control composites prepared from Bis-GMA or Bis-MEPP/ and TEGDMA in the same ratio. These composites contained 70 wt% of silanized silica filler. The depths of cure of the experimental composites except for one were significantly greater than those of the control composites. The mechanical properties of the experimental composites were comparable to those of the control composites with a few exceptions, but the difference in the mechanical properties between these exceptional composites and the control was small. The water sorption of the experimental composites was markedly lower than that of the composite containing Bis-GMA and comparable to that of the composite containing Bis-MEPP. These five fluorinated monomers are considered useful as the matrix monomer of light-cured composite resins.     

Visible light cured resin. Chronological change in mechanical properties of matrix resin immersed in MeOH

Monomer composition was examined to improve durability of matrix resin of visible light cured composite resin. As a monomer, five kinds of cyclophosphazene monomers, two kinds of commercial monomers and a mixture of commercial monomers were prepared to the visible light cured resins. The mechanical properties of these set products were examined with time after immersion in MeOH, an aging accelerating solvent. Compressive strength of the resins using cyclophosphazene monomers tended to decrease with time, but it increased in accordance with the increase of the number of polymerization group. Compressive strength of the resins using commercial monomers tended to decrease, but that using the BMPEPP monomer tended to increase with time. Yield point of the resins with the cyclophosphazene monomer 4 PN-(EMA)8 tended to increase with the time but that of the resins with other cases monomers decreased. The yield point of all three resins made using commercial monomers tended to decrease with time, but the rate of decrease was small for BMPEPP monomer. Compressive elastic modulus of the resins using cyclophosphazene monomers tended to increase with time when the number of polymerization group was 6-8, while it decreased when the number was 4-5. When commercial monomers were used, it tended to decrease with time, but the rate of decrease was small for the BMPEPP monomer. Transverse strength of the resins using cyclophosphazene monomers showed a tendency to decrease with time. When a commercial monomer was used, cracks appeared in the Bis-GMA+Tri-EDMA monomer after 7 days, and with the other two monomers, the transverse strength tended to decrease with time, though the rate of decrease was small for the BMPEPP monomer. Transverse elastic modulus tended to decrease with time, but the rate of decrease was small for the BMPEPP monomer.     

Mechanical properties and cure depth of UDMA-based composite resins

Mechanical properties and cure depth of visible light-cured composite resins based on six types of UDMA (IP-HEMA, IP-HPMA, XY-HPMA, MC-HPMA, UEDMA and UPDMA) monomers were investigated. Under wet conditions, the mechanical properties of the composite resins based on aliphatic UDMA (UEDMA and UPDMA) monomers were inferior to those based on the other UDMA monomers containing aromatic or cyclohexane rings in their chemical structures. The cure depth for these UDMA-based composite resins increased with increasing irradiation time. The composite resin based on the XY-HPMA monomer showed a cure depth and transmission coefficient superior to the other composite resins.     

Physicochemical properties of dental resins formulated with amine-free photoinitiation systems

ObjectiveTo assess the mechanical properties of two different dimethacrylate resin blends containing the photosensitizer camphorquinone (CQ) alone or in combination with one or more synergists including an amine and/or an iodonium.MethodsTwo co-monomer resin blends were formulated using Bis-GMA/TEGDMA and UDMA/TEGDMA, both at 1:1 mass ratio. Each resin blend was divided into four groups, comprising the following four photoinitiation systems: (1) CQ + 2-(dimethylamino)ethyl methacrylate (DMAEMA); (2) CQ + DMAEMA + bis(4-methyl phenyl)iodonium hexafluorophosphate (BPI); (3) CQ; and (4) CQ + BPI. Materials were evaluated for polymerisation kinetics, water sorption, solubility, flexural strength and modulus.ResultsBisGMA/TEGDMA with CQ showed minimal and insignificant degree of conversion and was not tested for water sorption/solubility and mechanical properties. The ternary system (i.e., CQ + DMAEMA + BPI), promoted the highest degree of conversion for each monomer blend. The resins containing amine had higher mechanical properties than the amine free. However, the UDMA amine free resins exhibited greater flexural strength and modulus than the corresponding amine free BisGMA resins. BisGMA/TEGDMA containing CQ + DMAEMA or CQ + BPI had significantly higher water sorption and solubility than the other groups.SignificanceResins containing amine presented better properties than the amine-free systems. The addition of iodonium salt (BPI) improved the degree of conversion of the resins, even without an amine co-initiator. The amine-free initiator system (CQ + BPI) was more effective when used with UDMA versus BisGMA based-resins respectively.     

Durability of commercial composite resin. Chronological change in transverse strength and transverse elastic modulus of composite resin immersed in MeOH

The durability of visible light-cured composite resin was examined. Five kinds of commercial redox type composite resin and 7 kinds of visible light-cured composite resin were used and their base monomers were analyzed by HPLC. After the set products were immersed in MeOH, transverse strength and transverse elastic modulus were measured. Furthermore, the MeOH sorption, solubility in MeOH and main soluble component were examined. The main component of the base monomer in all 5 kinds of redox type was Bis-GMA. Seven kinds of visible light-cured composite resin consisted of 4 kinds of Bis-GMA (including BMPEPP) and 3 kinds of UDMA. Both cases of redox type and visible light-cured type of composite resin, when they were immersed in MeOH, transverse strength and transverse elastic modulus decreased. In the case of redox type (Clearfil posterior new bond), the decrease of transverse strength and transverse elastic modulus was small, that is, its base monomer was Bis-GMA, and large quantities of hybrid type filler were mixed. In the case of redox type, transverse strength and transverse elastic modulus showed a tendency to decrease with the increase of MeOH sorption. Solubility of 12 kinds of these composite resins was 0.25-4.78% and its main component in Pyrofil light bond A was BMPEPP, the residual were coincident with the main component of base monomer.     

Aging studies of light cured dimethacrylate-based dental resins and a resin composite in water or ethanol/water.

OBJECTIVE: To study the aging of neat resins, prepared from bis-GMA, UDMA, D(3)MA or a mixture of bis-GMA/UDMA/D(3)MA (65/20/15 w/w/w), in water or 75% (v/v) ethanol/water 37 degrees C. Also the study of aging of Heliomolar RO, which is a radiopaque, microfilled, light cured composite, the resin matrix of which is the copolymer of bis-GMA/UDMA/D(3)MA (65/20/15 w/w/w). METHODS: Samples of neat resins and Heliomolar RO prepared by light curing were immersed in water or 75% (v/v) ethanol/water 37 degrees C, for 1, 7 or 30 days. Then the flexural and tensile strength were determined. The fractured surface of samples after the flexural tests was observed by scanning electron microscopy. RESULTS: Bis-GMA and copolymer resin did not showed any significant change in mechanical properties after immersion in water or 75% (v/v) ethanol/water 37 degrees C, for 30 days. On the contrary UDMA, D(3)MA and the composite Heliomolar RO showed a significant decrease. SIGNIFICANCE: The results obtained showed that the effect of aging in water or ethanol/water solution on mechanical properties of a light cured dimethacrylate resin depends on the chemical structure of resin. In the case of resin composite this effect depends on the filler-matrix bond strength.     

The effect of resin matrix composition on the polymerization shrinkage and rheological properties of experimental dental composites.

OBJECTIVES: This study was undertaken to evaluate the effect of the resin matrix composition of experimental composites on their polymerization shrinkage and rheological properties. METHODS: Six experimental composites consisting of varying ratios of Bis-GMA, TEGDMA, and UDMA were made. All composites had the same amount of filler (barium-aluminum-silicate glass, 76.5 wt.%) and initiator concentrations (camphorquinone, 1.7 wt.%). To investigate the effects of different resin matrices on the polymerization shrinkage, a newly developed measurement method was used. Using a rotational rheometer, a dynamic oscillatory shear test was undertaken to evaluate the rheological properties, including the storage shear modulus (G'), loss shear modulus (G'), loss tangent (tandelta), phase angle (delta), and complex viscosity (eta*) of the experimental composites as a function of frequency (0.1-10Hz). RESULTS: The polymerization shrinkage and complex viscosity of the experimental composites ranged from 2.61 to 3.88 vol.% and from 3.8 to 181.4Pas, respectively. The experimental composite composed of 17.5% Bis-GMA and 4.4% TEGDMA showed the lowest shrinkage and highest viscosity. The composite composed of 8.7% Bis-GMA and 13.1% TEGDMA showed the highest shrinkage and lowest viscosity. With increasing TEGDMA content, the polymerization shrinkage increased but the viscosity decreased. The substitution of UDMA for TEGDMA reduced the shrinkage level but increased viscosity. There was an inverse relationship between the polymerization shrinkage and complex viscosity. All experimental composites exhibited pseudoplasticity. SIGNIFICANCE: Within the limitations of this study, resin matrix composition significantly affected the volumetric shrinkage and rheological properties of the experimental composites.     

Characterization of urethane-dimethacrylate derivatives as alternative monomers for the restorative composite matrix

ObjectiveThe aim was accomplished by a comparative analysis of the physicochemical properties of urethane-dimethacrylate (UDMA) monomers and their homopolymers with regard to the properties of basic dimethacrylates used presently in dentistry. The homologous series of UDMA were obtained from four oligoethylene glycols monomethacrylates (HEMA, DEGMMA, TEGMMA and TTEGMMA) and six diisocyanates (HMDI, TMDI, IPDI, CHMDI, TDI and MDI).MethodsPhotopolymerization was light-initiated with the camphorquinone/tertiary amine system. Monomers were tested for viscosity and density. Flexural strength, flexural modulus, hardness, water sorption and polymerization shrinkage of the polymers were studied. The glass transition temperature and the degree of conversion were also discussed.ResultsHEMA/IPDI appeared to be the most promising alternative monomer. The monomer exhibited a lower viscosity and achieved higher degree of conversion, the polymer had lower water sorption as well as higher modulus, glass temperature and hardness than Bis-GMA. The polymer of DEGMMA/CHMDI exhibited lower polymerization shrinkage, lower water sorption and higher hardness, however it exhibited lower modulus when compared to HEMA/TMDI. The remaining monomers obtained from HEMA were solids. Monomers with longer TEGMMA and TTEGMMA units polymerized to rubbery networks with high water sorption. The viscosity of all studied UDMA monomers was too high to be used as reactive diluents.SignificanceThe systematic, comparative analysis of the homologous UDMA monomers and corresponding homopolymers along with their physico-mechanical properties are essential for optimizing the design process of new components desirable in dental formulations. Some of the studied UDMA monomers may be simple and effective alternative dimethacrylate comonomers.     

Effect of monomer structure on the mechanical properties of light-cured composite resins

The effects of monomer structure on the mechanical properties of visible light-cured composite resins based on the seven types of aromatic dimethacrylates were investigated. The results of this study suggested that the mechanical properties of the composite resins were dependent upon the chemical structure of the dimethacrylate monomers employed. The composites based on dimethacrylates with hydroxy groups showed a relatively significant decrease in flexural strength, elastic modulus, and compressive proportional limit under wet conditions. The segmental mobility of dimethacrylate monomers considerably influenced the nature of cured composites. Bis-GMA-F-based composite showed superior mechanical properties to a conventional Bis-GMA-based material. The SEM observation of fractured surfaces revealed that failure mainly occurred through the resin matrix of the composite resins.     

Dimethacrylate monomers with varied fluorine contents and distributions.

OBJECTIVES: There are many unique properties associated with fluorinated polymers that make these materials attractive for use in the challenging oral environment. This study was devised to better define the influence of fluorine content and its structural distribution on properties of fluorinated resins and composites, especially with regard to their water-related and mechanical properties. METHODS: A series of fluorinated dimethacrylate monomers was prepared by reaction of aromatic diepoxides with fluoroalcohols and subsequent conversion of the resulting diols to the methacrylates. Composites based on monomer systems comprised of the fluorinated monomers with 1,10-decamethylene dimethacrylate and reinforced with silanized quartz filler were evaluated for conversion, water contact angle, water sorption and diametral tensile strength. RESULTS: By selection of reactants, fluorine was introduced as trifluoromethyl groups, extended fluoroalkyl pendant chains, or combinations of the two. Photopolymerization conversion among the experimental composites was generally equal to or greater than that of a conventional Bis-GMA/TEGDMA composite. While the water contact angles generally increased with fluorine content, no correlation was obtained between fluorine content and water sorption of the composites. The mechanical strength of the fluorinated composites showed a general decline with increasing fluorine content and consistent variations due to specific structural features. SIGNIFICANCE: A versatile route to fluorinated dimethacrylates with diverse structural and fluorine distribution patterns is presented. Composites from these monomers are very hydrophobic but have relatively low mechanical strength. The monomers described can be considered as useful additives to moderate the water sorption of conventional resins. However, the results of this study point to specific fluorinated resin structures that are expected to provide a more optimal balance between hydrophobicity and mechanical strength that will improve the long-term performance of dental composites.     

Monomer composition and bond strength of light-cured 4-META opaque resin

A light-cured opaque resin was prepared with 4-(2-methacryloxyethoxycarbonyl) phthalic anhydride (4-META), bifunctional methacrylates, and titanium dioxide (TiO2). The relation between monomer composition and bond strength was examined with seven methacrylate monomers. Methyl methacrylate (MMA) was useful as a solvent of 4-META. However, it was not sufficiently cured by photo-initiator. The bond strength of a triethyleneglycol dimethacrylate (TEGDMA)-based composition was superior to other monomer-based compositions after repeated thermocycles. 1,6-bis(methacryloxy-2-ethoxycarbonyl-amino)-2,4,4-trimethylhex ane (UDMA) effectively provided viscosity to the composition. The prepared opaque resin consisted of 4-META/MMA-TEGDMA primer, TEGDMA-UDMA-based monomer, and titanium dioxide. This opaque resin bonded strongly to alumina-blasted cobalt-chromium alloy. The light-cured 4-META opaque resin may be useful for bonding prosthodontic composite to metal frameworks.     

Evaluation of methylene lactone monomers in dental resins.

alpha-Methylene-gamma-butyrolactone (MBL), which can be described as the cyclic analog of methyl methacrylate, exhibits greater reactivity in free radical polymerizations than conventional methacrylate monomers. Unfilled resin formulations composed of Bis-GMA/MBL or Bis-GMA/TEGDMA/MBL were light-cured. The effect of the more reactive methylene lactone monomer on mechanical properties and the degree of conversion of the polymers was examined. The infrared absorption bands for the carbon-carbon double bonds of MBL and the methacrylate monomers are well resolved and allow the conversion of each component to be calculated individually. The incorporation of a small amount of MBL (5 w/o) to Bis-GMA significantly increased the conversion; however, additional MBL (10 to 30 w/o) did not further increase the Bis-GMA conversion level. This appears to indicate an incompatibility between MBL and the bulky Bis-GMA monomer. Addition of 10 w/o MBL to Bis-GMA/TEGDMA (7:3) resulted in a cured resin with 71% methacrylate and 75% overall conversion efficiencies compared with the 57% conversion of the control formulation. The diametral tensile and the transverse strengths were approximately 10% greater for the MBL resin compared with the Bis-GMA/TEGDMA control; however, these differences were not statistically significant. The synthesis and polymerization of several substituted methylene lactones was also studied.     

Improvements to light transmittance in light-cured composite resins by the utilisation of low refractive index dimethacrylates

In an effort to improve the light transmittance of light-cured composite resins while avoiding degradation of their physical properties, 4 dimethacrylates having low refractive indices and a bulky backbones such as alicyclic or fluorine-substituted bisphenol groups were synthesized. The depths of cure and physical properties of 6 experimental composite resins containing these new monomers were, then, examined and compared to those of 3 control composite resins containing UDMA, BisMEPP, or BisGMA. The depths of cure of the experimental group containing the synthesized monomers were greater than those of the control group with the exception of the composite containing UDMA. The depth of cure increased as the difference between the refractive indices of the matrix monomer and silica filler decreased. The physical properties of 2 composites in the experimental group were comparable to those of the control group. The matrix monomers of these 2 composites were a mixture of 4,8-dimethacryloxymethylene tricyclo [5.2.1.0] decane or 2,2-bis (4-methacryloxyethoxy phenyl) hexafluoropropane and TEGDMA in a molar ratio of 1/1.     

螺环原酸酯对牙科基体树脂的改性研究

目的：用螺环原酸酯膨胀单体对牙科BisS-GMA基体树脂进行改性的研究。方法：分别以BisS-GMA和Bis-GMA作树脂基质,TEGDMA为稀释单体,加入和不加入螺环原酸酯膨胀单体,配制四种基体树脂。以CQ/DMAEMA为光引发体系,光固化后测定并比较其体积收缩率、聚合转化率、粘接拉伸强度和固化时间。结果：含膨胀单体的BisS-GMA基体树脂的体积收缩率较低,聚合转化率和粘接拉伸强度较高,且固化时间合适。结论：螺环原酸酯膨胀单体的开环聚合反应能使BisS-GMA基体树脂的体积收缩率显著降低,并能提高其聚合转化率和粘接拉伸强度。     

The relationship between monomer composition and physical properties of light-cured opaque resin.

Light-cured opaque resins were prepared using four types of monomer liquids and titanium dioxide powder. This study investigated the relationship between the monomer composition and the physical properties of light-cured opaque resin. Depth of cure, KHN, residual monomer eluent, and bond strength between the opaque resin and cobalt-chromium alloy were measured. The physical properties of triethyleneglycol dimethacrylate (TEGDMA)-based compositions were superior to those of methyl methacrylate (MMA)-based compositions. Viscosity of the opaque resin's liquid monomer was enhanced by 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimeth ylhexane (UDMA). The TEGDMA-based light-cured opaque resins showed excellent physical properties and may be clinically acceptable in bonding prosthodontic composite to metal frameworks.     

Synthesis, characterization and evaluation of urethane derivatives of Bis-GMA.

OBJECTIVES: The aims of the study were to synthesize derivatives of Bis-GMA having pendant n-alkyl urethane substituents and to characterize and evaluate their physicochemical properties. METHODS: Stoichiometric amounts of Bis-GMA and n-alkyl isocyanates were reacted in dichloromethane with dibutyltin dilaurate as a catalyst. Volumetric shrinkage, water uptake, degree of vinyl conversion, refractive index and viscosity of resulting urethane monomers and those of Bis-GMA were measured. The flexural strengths of their corresponding homopolymers and that of Bis-GMA were also measured. RESULTS: These types of urethane derivatives of Bis-GMA exhibited lower viscosities and were more hydrophobic than Bis-GMA. Generally, the viscosity of these experimental monomers decreased with increasing chain length of the alkyl urethane substituent. Photopolymerization of the new monomers gave high degrees of vinyl conversion compared to Bis-GMA. The experimental monomers also yielded polymers with lower polymerization shrinkages at equivalent degrees of vinyl conversion, than Bis-GMA. The refractive indices of these urethane derivatives were similar to Bis-GMA, but the flexural strengths of their polymers were lower than that of the Bis-GMA homopolymer, decreasing with increasing chain length of the alkyl urethane substituent. SIGNIFICANCE: Because of their excellent overall properties, these new derivatives of Bis-GMA have potential as dental monomers that can improve many properties of resin based dental materials that utilize methacrylate monomer systems.     

Volume contraction in photocured dental resins: the shrinkage-conversion relationship revisited.

Polymerization shrinkage and degree of conversion (DC) of resin composites are closely related manifestations of the same process. Ideal dental composite would show an optimal degree of conversion and minimal polymerization shrinkage. These seem to be antagonistic goals, as increased monomer conversion invariably leads to high polymerization shrinkage values. OBJECTIVES: This paper aims at accurately determining the polymerization volume contraction of experimental neat resins and to link it to the number of actual vinyl double bonds converted in single ones instead of, as generally done, to the degree of conversion. METHODS: Different mixtures of Bis-GMA/TEGDMA (traditionally used monomers) were analyzed. Contraction of the polymers was determined by pycnometry and the use of a density column. DC was determined by the use of Raman spectrometry. RESULTS: An univocal relationship has been found between the volume contraction and the actual number of vinyl double bonds converted into single ones. A contraction value of 20.39 cm3/mole (of converted C=C) was deduced from 27 measurements. SIGNIFICANCE: This relationship helps in finding solutions to the polymerization shrinkage problem. A reduction of the polymerization shrinkage due to the chemical reaction may obviously be expected from the addition of molecules allowing a decrease in the number of double bonds converted per unit volume of resin matrix, while maintaining the degree of conversion (of Bis-GMA and TEGDMA) and thus the mechanical properties. Further research will be directed at this objective.