• Macromolecular Research
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• 제13권3호
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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.

• Restorative Dentistry and Endodontics
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• 제27권2호
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• pp.135-141
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• 2002

Objectives : The aim of this study is to evaluate the effect of light intensity variation on the polymerization rate of composite resin using IB system (the experimental equipment designed by Dr. IB Lee) by which real-time volumetric change of composite can be measured. Methods : Three commercial composite resins [Z100(Z1), AeliteFil(AF), SureFil(SF)] were photopolymerized with Variable Intensity Polymerizer unit (Bisco, U.S.A.) under the variable light intensity (75/150/225/300/375/450mW$^2$) during 20 sec. Polymerization shrinkage of samples was detected continuously by IB system during 110 sec and the rate of polymerization shrinkage was obtained by its shrinkage data. Peak time(P.T.) showing the maximum rate of polymerization shrinkage was used to compare the polymerization rate. Results : Peak time decreased with increasing light intensity(p<0.05). Maximum rate of polymerization shrinkage increased with increasing light intensity(p<0.05). Statistical analysis revealed a significant positive correlation between peak time and inverse square root of the light intensity (AF:R=0.965, Zl:R=0.974, SF:R=0.927). Statistical analysis revealed a significant negative correlation between the maximum rate of polymerization shrinkage and peak time(AF:R=-0.933, Zl:R=-0.892, SF:R=-0.883), and a significant positive correlation between the maximum rate of polymerization shrinkage and square root of the light intensity (AF:R=0.988, Zl:R=0.974, SF:R=0.946). Discussion and Conclusions : The polymerization rate of composite resins used in this study was proportional to the square root of light intensity Maximum rate of polymerization shrinkage as well as peak time can be used to compare the polymerization rate. Real-time volume method using IB system can be a simple alternative method to obtain the polymerization rate of composite resins.

• 한국염색가공학회지
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• 제7권1호
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• pp.43-50
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• 1995

The grafting of methacrylonitrile(MAN) onto Kevlar 49 filament surface was carried out by anionic polymerization using sodium methylsulfinylcarbanion formed from sodium hydride and dimethyl sulfoxide(DMSO). The effects of reaction conditions on the grafting percentage(GP) and on the tensile strength of the fiber were investgated. GP marktedly increased with increasing metalation time, and NaH concentration, polymerization temperature and time. The tensile strength of fiber decrased with increasing metalation time, and NaH concentration, polymerization temperature and time. The optimum conditions to increase over 40% of GP with below 10% reduction rate of tensile strength of fiber : NaH concentration ; 30.6 mmol/l/0.5g Kevlar, metalation time : 10min, polymerization tempera- ture : 5$0^{\circ}C$, polymerization time: 20 sec, monomer concentration : 1.12mol/l/0.5g Kevlar.

• 폴리머
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• 제39권3호
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• pp.365-369
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• 2015

본 연구에서는 Al 화합물인 methylaluminoxane(MAO)를 이용하여 L-lactide의 벌크중합 및 용액중합을 실시하였다. 촉매 투입량에 따른 벌크중합 결과, 투입량이 증가할수록 전환율이 증가하였다. 분자량은 촉매 투입량이 0.15 mmol일 때 60800 g/mol로 가장 높은 분자량을 얻었으며 그 이상의 투입량에서는 분자량이 감소하였다. Turnover frequency(TOF)값의 경우 촉매 투입량이 0.15 mmol일 때 가장 크고 촉매 투입량이 증가할수록 감소하였다. 용액중합에서는 30분 가량 induction time이 존재하였다. 중합 시간에 따라 3시간까지 전환율이 선형적으로 증가하였으며 6시간일 때 54700 g/mol로 가장 높은 분자량을 얻었다.

• Restorative Dentistry and Endodontics
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• 제26권2호
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• pp.134-140
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• 2001

The polymerization shrinkage of composite resins is an important drawback although the composites have many advantages-more esthetic and conservative than metallic restoratives etc. The purposes of this research were to develop a new measurement method and to manufacture an instrument that can measure the initial dynamic volumetric shrinkage of composite resins during polymerization. The instrument was basically an electromagnetic balance that constructed with a force transducer using position sensitive photo detector(PSPD) and a negative feedback servo amplifier of proportional-derivative(PD) controller. The volumetric change of composites during polymerization was detected continuously as buoyancy change in distilled water by means of Archimedes's principle. It was converted to continuous electrical voltage signal in real time. The signal was properly conditioned and filtered and then it was stored in computer by a data acquisition(DAQ) board. By using this electronic instrument. the dynamic patterns of the polymerization shrinkage of eight commercial(Z-100, DenFil, AeliteFil, Z-250, P-60, SureFil, Synergy compact, and Tetric ceram) composite resins were measured and compared. The results were as follows. 1. From this project of developing instrument, the ability has been achieved that can acquire and process data of electrical signal transformed from various physical phenomenon by using temperature, displacement. photo. and force transducer. As a consequence, the instrumentation and measurement system used to analyze the physical characteristics of various dental materials in dental research field can be designed, manufactured and implemented in lab. 2. This instrument has some advantages. It was insensible to temperature change and could measure true dynamic volumetric shrinkage in real time without complicated process. It showed accuracy and high precision results with small standard deviation. 3. The polymerization shrinkage of composites was significantly different between brands and ranged from 2.47％ to 3.89％, The order of polymerization shrinkage was as follows, in order of increasing shrinkage, SureFil, P60, Z250, Z100, Synergy compact. DenFil, Tetric ceram, and AeliteFil. 4. The polymerization shrinkage rate per unit time, dVol％/dt, showed that the instrument can provide an indirect research method for polymerization reaction kinetics.

• Restorative Dentistry and Endodontics
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• 제10권1호
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• pp.145-152
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• 1984

The purpose of this study was to compare combinations of the four visible light irradiating appliances (Translux, Heliomat, Pluraflex HL 150, Omega) and the four visible light activated composite resins (Durafil, Heliosit, Plurafil-super, Silux) to determine the depth of polymerization of each combination. Twenty samples were made with Durafil. Five samples were polymerized for 20 seconds using Translux, five with Heliomat, five with Pluraflex HL 150, five with Omega. Twenty samples were made with Heliosit, twenty with Plurafil-super, and twenty samples with Silux. A 20-second polymerization time was applied with each of 4 visible light irradiating appliances to 5 samples of each material. Eighty samples were treated in a like manner, but polymerization was extended to 40 seconds. Depth of polymerization were measured with caliper. The results were as follows. 1) Of the two time exposures, 40-second exposure provided a significantly greater depth of polymerization than 20-second for each light with each material. 2) Durafill-Translux system showed minimum depth of polymerization, and Plurafil-Pluraflex system showed maximum depth of polymerization. 3) Visible light irradiating appliances were able to harden the resins cured by tire visible lights of other makers' apparatuses. 4) In all circumstances, depth of polymerization was between 3.0-3.8mm.

• 한국의류학회지
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• 제13권1호
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• pp.89-97
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• 1989

Graft polymerization of MMA onto cotton fiber was carried out in two ways, two step graft polymerization and one step emulsion graft polymerization, using tetravalent cerium ion as an initiator. At two step graft polymerization, the first step was the pretreatment of cotton fiber with an aqueous initiator solution and the second was the grafting pretreated cotton fiber in the monomer solution. In case of one step emulsion graft polymerization, MMA was emulsified with SLS in initiator solution. Under the various graft polymerization conditions, graft yield, graft efficiency and from the Arrhenius plot the apparent activation energy were compared. The results of this study were as follows: 1. Graft yield and graft efficiency of emulsion graft polymerization were higher than those of two step graft polymerization. 2. In case of two step graft polymerization, graft yield was affected by the pretreatment time of cotton fiber with an aqueous initiator solution. And graft yield of emulsion graft polymerization was increased with the concentration of emulsifier below cmc of SLS and was decreased thereafter. 3. Elevation of temperature resulted increase in graft yield for both grafting methods. The apparent activation energy of emulsion graft pelymerzation was lower than that of two step graft polymerization. 4. Increased reaction time increased in graft yield, but decreased in graft efficiency. 5. Moisture regain of grafted cotton was decreased with graft yield.

• Korean Chemical Engineering Research
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• 제49권5호
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• pp.676-680
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• 2011

스티렌과 메틸아크릴레이트(methyl acrylate, MA)를 원자라디칼이동 중합(atom radical transfer polymerization, ATRP)에서 주요한 중합공정 조건인 투입되는 MA 몰분율, 중합 온도, 중합 시간이 미치는 영향을 조사하였다. MA 몰분율이 증가할수록 분자량은 증가하고 중합시간이 3시간일 때 중합용액의 초기 모노머 몰 비와 생성되는 고분자의 조성비가 거의 선형 관계를 갖는다. 중합시간이 증가함에 따라 공중합체의 분자량은 증가하고, 공중합체의 MA 조성비가 감소함을 알 수 있다. 이를 통해 스티렌-MA 공중도 ATRP의 리빙 라디칼 중합 특징을 보이고 있음을 알 수 있다. 중합온도가 증가함에 따라 공중합체의 분자량은 크게 증가하고, 특히 $110^{\circ}C$의 고온에서 공중합체 내에 MA 조성비가 크게 증가함을 볼 수 있다.

• Journal of Industrial and Engineering Chemistry
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• 제68권
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• pp.1-5
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• 2018

In this study, we designed and synthesized novel thermal radical initiators of BTAP (1-phenyl-3,3-dipropyltriazene), BTACP (1-(phenyldiazenyl)pyrrolidine), BTACH (1-(phenyldiazenyl)piperidine), and BTACH7 (1-(phenyldiazenyl)azepane) based on a triazene moiety to provide a thermal initiator for radical polymerization. The synthetic method is valuable due to the simplicity. In addition, the synthesized thermal initiator did not affect the color of the polymer. Among the four initiators, the polymerization time for the BTACH of the 6-membered ring decreased by 67%, as opposed to the polymerization time without initiator. Conversion after polymerization was over 92%. DSC experiments also showed that the initiator with hexagonal rings had the lowest peak polymerization temperature of $160^{\circ}C$. Our study suggests a promising new initiator system that is effective for radical polymerization.

• 대한치과기공학회지
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• 제35권2호
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• pp.127-136
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• 2013

Purpose: In order to find out the impact of changes in polymerization conditions of orthodontic acrylic resin on maximum load. Methods: While maintaining mixing ratio 3:1 of polymer and monomer in spray-on way in the production condition of polymerization temperature $25^{\circ}C$ or $37^{\circ}C$ for 10 minutes or 30 minutes of polymerization time by pressure $3kfg/cm^2$ or $6kfg/cm^2$ in the lab maintaining $25^{\circ}C$ of room temperature, the change in maximum load rise rate was tested by producing 5 acrylic resin specimens for orthodontics per group to meet the standards of $25mm{\times}2mm{\times}2mm$ and using INSTRON with the 3rd bar 2mm in diameter and parallel support bending device of $15{\pm}0.1mm$ as test equipment showing 30.00mm/min of crosshead speed, $50{\pm}16$ N/min of load ratio in the laboratory of $24^{\circ}C$ room temperature and as a result, the following results were obtained. Results: 1. When increasing pressure from $3kfg/cm^2$ to $6kfg/cm^2$, maximum load was lowered by -4.285%. 2. When increasing polymerization time from 10 minutes to 30 minutes, maximum load rose by 3.848%. 3. When increasing polymerization temperature from $27^{\circ}C$ to $37^{\circ}C$, maximum load rose by 5.854%. Conclusion: Considering the above test results that polymerization time and polymerization temperature when polymerizing acrylic resin for orthodontics according to changes in working conditions had an impact on the rate of rise of maximum load values but the rate of rise was lowered when increasing pressure from $3kfg/cm^2$ to $6kfg/cm^2$, we came to a conclusion that high pressure more than necessary does not affect the rate of rise of maximum load.