• Macromolecular Research
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• v.13 no.3
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• pp.187-193
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• 2005

The TEMPO-mediated living free-radical bulk and dispersion polymerization of styrene in the presence of camphorsulfonic acid (CSA) are investigated. In the absence of TEMPO and CSA in the bulk polymerization, a conversion of $93\%$ is achieved within 6 hr of polymerization. When only TEMPO is involved in this polymerization, the pseudo-living free-radical polymerization is well achieved, however, the polymerization rate becomes quite slow. This retardation of the polymerization rate is solved by the addition of a low concentration of CSA. In the TEMPO-mediated dispersion polymerization in the presence of CSA, similar trends in the conversion, kinetics, and PDI are observed as those observed in the case of bulk polymerization. When only TEMPO is used in the dispersion polymerization, the resulting particle size becomes quite broad, due to the prolonged polymerization time. However, when a 1.0 molar ratio of CSA to TEMPO is added to the TEMPO-mediated dispersion polymerization, fairly mono-disperse PS microspheres having an average size of 5.83 $\mu$m and a CV of 3.4$\%$ are successfully obtained, due to the narrow molecular weight distribution of the intermediate oligomers and shortening of the polymerization time. This result indicates that the addition of CSA to the TEMPO-mediated bulk and the use of dispersion polymerization not only shortens the polymerization time, but also greatly improves the uniformity of the microspheres.

• Macromolecular Research
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• v.13 no.3
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• pp.236-242
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• 2005

Three dithioester-derived carboxyl acid functionalized RAFT(reversible addition-fragmentation chain transfer) agents, viz. acetic acid dithiobenzoate, butanoic acid dithiobenzoate and 4-toluic acid dithiobenzoate, were used in the RAFT bulk polymerization of styrene, in order to study the effects of the R-group structure on the living nature of the polymerization. By conducting the polymerization with various concentrations of the RAFT agents and at different temperatures, it was found that the R-group structure of the RAFT agents plays an important role in the RAFT polymerization; the bulky structure and radical stabilizing property of the R-group enhances the living nature of the polymerization and allows the polymerization characteristics to be well controlled.

• Proceedings of the Korean Fiber Society Conference
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• 2003.04a
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• pp.13-16
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• 2003

Vinyl acetate monomer can be polymerized through bulk, solution, emulsion, and suspension polymerization processes. However, in the preparation of PVA from bulk or solution polymerization, there are several technical limitations for obtaining high yield and high molecular weight simultaneously. Thus, the improvement of polymerization method is necessary to prepare the PVA with high yield and high molecular weight because that the difficulty in control of high viscosity and in removal of the heat of polymerization, which might lead to side reactions like branching. (omitted)

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.236-242
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• 2014

Isospecific propylene polymerization behavior of meta- and para-Lewis base (E) functionalized unbridged zirconocenes ($[1-(E_n-Ph)-3,4-Me_2C_5H_2]_2ZrCl_2$, E = $NMe_2$, OMe; n = 1 or 2) was investigated under bulk conditions. Catalytic activity of the zirconocenes, and molecular weight and isotacticity of polypropylenes are found to be dependent on the position and number of the Lewis base functional groups in the zirconocenes. All the crude polypropylenes possess a broad molecular weight distribution and multi-melting transitions, indicating an involvement of multi-catalytic active species in the polymerization. The highest [mmmm] value of an isotactic portion of the polypropylenes reached 89%, which is higher than that (85%) from the well-known $C_2$-symmetric EBIZr (rac-$Et(Ind)_2ZrCl_2$) catalyst. These results support that the in situ generated, rigid rac-like cation-anion pair through the Lewis acid-base interactions between the functional groups of zirconocenes and methylaluminoxane anion is effective in the formation of isotactic polypropylene under bulk propylene polymerization conditions.

• Journal of dental hygiene science
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• v.23 no.2
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• pp.123-131
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• 2023

Background: As a restorative material used to treat dental caries, the light-curing type resin is widely used, but it has the disadvantage of polymerization shrinkage. The Bulk-Fill composite resin was developed to solve these shortcomings, but the existing research mainly focused on comparing the physical properties of a composite resin and a Bulk-Fill resin. A study on the light curing time and distance of the Bulk-Fill resin itself tend to be lacking. Methods: This study compares the surface microhardness of specimens prepared by varying the light curing time and distance of smart dentin replacement (SDR) as a flowable Bulk-Fill resin and Tetric N-ceram as a packable Bulk-Fill resin, and confirms the polymerization time and distance that becomes the optimum hardness. To determine the hardness of the specimen, it was measured using the Vickers Hardness Number (Matsuzawa MMT-X, Japan). Results: In SDR, the surface microhardness decreased as the distance increased in all time groups in the change distance from the curing tip. In the change of light curing time with respect to the distance from curing tip, the surface microhardness increased as the time increased. In Tetric N-ceram, the surface microharness showed no significant difference in the change of the distance of curing tip in the group of 20 and 60 second. But in the group of 10 and 40 seconds, decreased as the distance increased. The surface microharness increased as the light curing time increased in all distance groups. Conclusion: When using SDR and Tetric N-ceram in clinical practice, it is considered that as the distance from the polymerization reactor tip increases, a longer light curing time than the polymerization time recommended by the manufacturer is required.

• Journal of the korean academy of Pediatric Dentistry
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• v.46 no.1
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• pp.1-9
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• 2019

The aim of this study was to compare the degree of conversion and polymerization shrinkage of low and high viscosity bulk-fill giomer-based and resin-based composites. Two bulk-fill giomer (Beautifil Bulk Restorative (BBR), Beautifil Bulk Flowable (BBF)), two bulk-fill (Tetric N-Ceram Bulk-fill (TBF), SureFil SDR flow (SDR)) and two conventional resin composites (Tetric N-Ceram (TN), Tetric N-flow (TF)) were selected for this study. The degree of conversion was measured by using Fourier transform infrared spectroscopy. Polymerization shrinkage was measured with the linometer. For all depth, BBR had the lowest degree of conversion and SDR had the highest. At 4 mm, the degree of conversion of low and high viscosity bulk-fill giomer resin composites was lower than that of bulk-fill resin composites (p < 0.05). At the depth between 2 mm and 4 mm, there were significant difference with TBF, TN and TF (p < 0.05), while no significant difference in the degree of conversion was measured for BBR, BBF and SDR. Polymerization shrinkage of six resin composites decreased in the following order: TF > SDR > BBF > TBF > TN and BBR (p < 0.05). Polymerization shrinkage of bulk-fill giomer resin composites was lower than that of bulk-fill resin composites (p < 0.05). From this study, it is found that the bulk-fill giomer resin composites and TBF were not sufficiently cured in 4 mm depth. The degree of conversion of low and high viscosity bulk-fill giomer resin composites was significantly lower than bulk-fill resin composites in both 2 mm and 4 mm depths. Therefore, such features of bulk-fill giomer resin composites should be carefully considered in clinical application.

• The Journal of the Korean dental association
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• v.57 no.3
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• pp.162-168
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• 2019

Composite resin restorations in posterior teeth are increasing due to the aesthetic needs of patients and the development of materials. This trend will accelerate in line with domestic insurance policies. However, resin composites generate stresses due to their contraction during the polymerization process. To reduce the polymerization shrinkage stress of resin composites, incremental layering technique has been recommended for decades. This technique reduces stress at the cavity wall interface and allows a more efficient light curing of the material. Bulk-fill resin composites have been designed to simplify the restorative technique because they can be placed into cavities in a single increment of 4-5mm. The simplification of the operative procedures is desirable in clinical daily practice. In this context, bulk-fill resin composites are an attractive alternative for posterior restorations. However, a clearer understanding of the clinical performance of this relatively new class of materials in comparison to conventional resin composites is required. Based on previous studies, the aim of the current review was to present the clinical criteria for the use of bulk-fill composites in direct restorations of posterior teeth.

• Polymer(Korea)
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• v.39 no.3
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• pp.365-369
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• 2015

In this study, the bulk and solution polymerizations of L-lactide using an aluminium compound, methylaluminoxane (MAO), were performed. In the bulk polymerization, the conversion of polymerization was increased with increasing the amount of catalyst in feed. The largest molecular weight (Mw), 60800 g/mol, was shown at the MAO amount in feed of 0.15 mmol, and Mw was decreased above 0.15 mmol of MAO in feed. At the 0.15 mmol of MAO in feed, turn of frequency (TOF) was the highest, and it was decreased with increasing MAO amount in feed. In the solution polymerization, the induction time of 30 min was shown. The conversion of polymerization was linearly increased with the polymerization time, and the highest Mw, 54700 g/mol, was achieved at the polymerization time of 6 h.

• Journal of the korean academy of Pediatric Dentistry
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• v.43 no.4
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• pp.365-373
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• 2016

Composites are the most useful restorative material. However, composites have some disadvantages such as polymerization shrinkage, long working time, and susceptibility to water and contamination, which are stood out more especially when treating children. To solve these problems, bulk-fill composites have been developed. The aim of this study is to compare mechanical properties of bulk-fill and conventional composites. Bulk-fill composites (SureFil SDR flow (SDR), Tetric N-Ceram bulk fill (TBF)) and conventional composites (Filtek Z-350 (Z-350), Unifil Flow (UF), Unifil Loflo Plus (UL)) were used. The Vickers hardness tester was used to measure the microhardness of materials, and Fourier transform infrared spectroscopy was used to measure the degree of conversion. Polymerization shrinkage was measured by using a linometer. Flexural and compressive properties were measured by using the universal testing machine. Data were statistically analyzed by ANOVA and Scheffe's post hoc test. The level of significance was set to p < 0.05. Most conventional composites showed higher microhardness than bulk-fill composites. However, bulk-fill composites showed a higher top/bottom microhardness ratio than conventional composites. Bulk-fill composites showed a higher top/bottom degree of conversion ratio than conventional composites. The polymerization shrinkage was highest in UL and lowest in Z-350. The polymerization shrinkage of flowable composites was higher than that of non flowable composites. The compressive properties were highest in Z-350 and lowest in SDR and UL. In terms of flexural properties, Z-350 was the highest. However, none of the bulk-fill composites exhibited mechanical properties as good as those of conventional composites. Nonetheless, the ratio of microhardness and degree of conversion, which are important properties of bulk filling, were higher in bulk-fill composites. Therefore, the bulk-fill composites might be considered suitable restorative materials in pediatric dentistry.

• Restorative Dentistry and Endodontics
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• v.45 no.3
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• pp.32.1-32.12
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• 2020

Objectives: To evaluate the polymerization efficiency of a matrix-modified bulk-fill composite, and compare it to a conventional composite which has a similar filler system. The degree of conversion (DC%) and monomer elution were measured over different storage periods. Additionally, fillers' content was examined. Materials and Methods: Cylindrical specimens were prepared, in bulk and incrementally, from Filtek Bulk Fill (B) and Filtek Supreme XTE (S) composites using a Teflon mold, for each test (n = 6). Using attenuated total reflection method of Fourier transformation infrared spectroscopy, DC% was measured after 24 hours, 7 days, and 30 days. Using high-performance liquid chromatography, elution of hydroxyethyl methacrylate, triethylene glycol dimethacrylate, urethane dimethacrylate, and bisphenol-A glycidyl dimethacrylate was measured after 24 hours, 7 days and 30 days. Filler content was examined by scanning electron microscopy (SEM). Data were analyzed using 2-way mixed-model analysis of variance (α = 0.05). Results: There was no significant difference in DC% over different storage periods between B-bulk and S-incremental. Higher monomer elution was detected significantly from S than B. The elution quantity and rate varied significantly over storage periods and between different monomers. SEM images showed differences in fillers' sizes and agglomeration between both materials. Conclusions: Matrix-modified bulk-fill composites could be packed and cured in bulk with polymerization efficiency similar to conventional composites.