• 한국환경과학회지
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• 제20권3호
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• pp.385-394
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• 2011

Organotin compounds (OTs), namely butyltins compounds (BTs) and phenyltin compounds (PhTs), were measured in surface and core sediments collected in Jeju harbor. The horizontal and vertical distribution was examined and the relationship between the concentration of OTs and organic matter content and particle size distribution was also studied. BTs were detected in significant concentrations in sediments inside Jeju harbor. PhTs were detected in very low concentrations, compared to BTs. The main species in BTs and PhTs were dibutyltin (DBT) and monobutyltin (MBT), monophenyltin (MPhT), respectively. In the relationships between the concentrations of total BTs and organic carbon content, the significant correlations ($r^2$=0.4898 in surface sediments, $r^2$=0.53 in one core sediments) and no correlation in another core sediments obtained, which is estimated that the distribution of BTs in sediments were affected by several factors, such as their physicochemical properties including organic carbon content, and a tide, etc. In the relationships between the concentrations of total BTs and particle size (mud, sand, and gravel) in sediments, the concentrations of total BTs were higher in the sediments with higher mud content, indicating that higher BTs were distributed with increasing sediments of fine granules.

• Macromolecular Research
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• 제13권3호
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• pp.212-217
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• 2005

The pyrolysis kinetics of polyurethanes synthesized from polycaprolactone diol (PCL) and diisocyanate (HDI, $H_{12}MDI$) using catalysts such as dibutyltin dilaurate (DBTDL) were studied by a thermogravimetric (TG) technique, which involved heating the sample at the rates of 10, 20 and $30^{\circ}C$/min. The effect of the kind of diisocyanate and the hard segment contents on the activation energy and reaction order were examined at conversions ranging from 1 to $100\%$. The activation energies at first increased slowly with increasing conversion. Also, differential scanning calorimetry (DSC) was used to investigate the structural differences in each polyurethane. DSC can reveal the melting behavior, in terms of the glass transition temperature ($T_g$), which is known to vary as a function of the stoichiometry and processing conditions.

• 한국염색가공학회지
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• 제11권4호
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• pp.1-7
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• 1999

Urethane-acrylate propelymers for secondary coating of optical fiber and high - performance material were prepared from the 4,4'-diphenylmethane diisocyanate(MDI), poly(tetramethylene oxide)glycol(PTMG, Mw 650 or 1000), 1,6-hexanediol(HD), 2-hydroxyethyl acrylate(HEA), and dibutyltin dilaurate as a catalyst. UV-Curable polyurethane acrylates were formulated from the urethane-acrylate prepolymers, three types of reactive diluents(DTs) having mono-, di-, and trifunctional-phenoxyethyl acrylate(PEA), hexanediol diacrylate(HDDA), and trimethylolpropane triacrylate(TMPTA), and 1-hydtoxycyclohexyl phenyl ketone(Irgacure 184) as a photoinitiator. The UV-cured films of polyurethane acrylates were obtained by curing using a medium-pressure mercury lamp(U W/cm, $\lambda_{max}=365\;nm)$. In this work, the effects of molecular weights of polyol and diol with low molecular weight into polymer chain on mechanical and dynamic mechanical properties of UV-cured polyurethane acrylates were studied. The structure and properties of the films obtained from the UV photopolymerization of urethane-acrylate prepolymer were investigated by FT-IR spectroscopy, dynamic mechanical measurement, tensile testing, and X-ray diffractometry.

• Macromolecular Research
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• 제13권5호
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• pp.427-434
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• 2005

To improve the performance and reduce raw material costs, blocked isocyanates were prepared with mixture of blocking agents in many industries. Three blocked isocyanates (adducts) namely $\varepsilon$-caprolactam/benzotriazole-blocked 4,4'-diphenylmethane diisocyanate (MDI), toluene-2,4-diisocyanate (TDI) and 4,4'-dicyclohexyl-methane diisocyanate ($H_{12}$MDI) were synthesized. Six reference adducts were also prepared by blocking MDI, TDI, and $H_{12}$MDI with $\varepsilon$-caprolactam ($\varepsilon$-CL) or benzotriazole. The reactions were carried out in acetone medium and dibutyltin dilaurate (DBTDL) was used as a catalyst. The progress of the blocking reaction was monitored by IR spectroscopy. De-blocking temperatures (dissociation temperatures) of these adducts were studied using DSC and TGA and the results were correlated. As expected, the thermal analysis data showed that de-blocking temperature of blocked aromatic isocyanates was lower than that of the blocked aliphatic isocyanates. The low de-blocking temperature of blocked aromatic isocyanate could be due to electron withdrawing benzene ring present in the blocked isocyanates. It was also found that benzotriazole-blocked adducts de-blocked at higher temperature compared with $\varepsilon$-CL-blocked adducts.

• 한국환경과학회지
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• 제14권12호
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• pp.1141-1153
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• 2005

Butyltin compounds (BTs), namely tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT), were measured in surface and core sediments collected in 2001 inside Seogwipo Harbor, in order to evaluate their distribution characteristics. Seogwipo Harbor is one of major harbors of Jeju Island where a lot of shipping occurs and is designated as a trade port by the Korea Maritime and Port Law. BTs were detected in surface and core sediments of all stations and their concentrations in surface sediments were low, compared with to those in other sites of domestic and foreign countries. The main species among BTs was MBT, although there was a little difference with a survey site in surface sediments and in core sediments with depth. No or low correlations were obtained between organic matter or particles size of surface and core sediments and total BTs, indicating that these factors did not affect the distribution of BTs. It was estimated that more complex factors including BTs loads and surrounding sedimentary environments, affect the distribution of BTs. The high correlations between BTs indicated that DBT and MBT were mainly degraded from TBT based on antifouling paints of vessel etc. and other sources, such as DBT and MBT, could be ignored. The butyltin degradation indices ([DBT]+[MBT]/[TBT]) in surface sediments were in the range of $2.0\~3.8$ (mean 3.0), indicating that the parent compound, TBT, were inflowed into the surface sediments a long years ago, degraded and deposited. The sedimentation age of BTs contaminated core sediments could not estimated because the content of $^{210}pb$ activity were nearly all the same and so the sedimentation rate could not obtained.

• 공업화학
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• 제31권3호
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• pp.284-290
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• 2020

Energetic thermoplastic elastomers (ETPEs) based on glycidyl azide polymer (GAP) and carboxylated GA copolymers [GAP-ETPE and poly(GA-carboxylate)-ETPEs] were synthesized using isophorone diisocyanate (IPDI), dibutyltin dilaurate (DBTDL), 1,4-butanediol (1,4-BD), and soft segment oligomers such as GAP and poly(GA-carboxylate). The synthesized GAP-ETPE and poly(GA-carboxylate)-ETPEs were characterized by Fourier transform infrared (FT-IR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), universal testing machine (UTM), calorimetry and sensitivity towards friction and impact. DSC and TGA results showed that the introduction of carboxylate group in GAP helped to have better thermal properties. Glass transition temperatures of poly(GA-carboxylate)-ETPEs decreased from -31 ℃ to -33 ℃ compared to that of GAP-ETPE (-29 ℃). The first thermal decomposition temperature in poly(GA_0.8-octanoate_0.2)-ETPE (242 ℃) increased in comparison to that of GAP-ETPE (227 ℃). Furthermore, from calorimetry data, poly(GA-carboxylate)-ETPEs exhibited negative formation enthalpies (-6.94 and -7.21 kJ/g) and higher heats of combustion (46713 and 46587 kJ/mol) compared to that of GAP-ETPE (42,262 kJ/mol). Overall, poly(GA-carboxylate)-ETPEs could be good candidates for a polymeric binder in solid propellant due to better energetic, mechanical and thermal properties in comparison to those of GAP-ETPE. Such properties are beneficial to application and processing of ETPE.

• Animal cells and systems
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• 제11권1호
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• pp.1-8
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• 2007

Recently, we have shown that some endocrine disruptors, heavy metals, organotins and azoles suppressed steroidogenic enzymes such as P450 side-chain cleavage enzyme (P450scc) and aromatase in bullfrog ovarian follicles. In the present study, by using an amphibian ovarian follicle culture system, we examined the effects of these endocrine disruptors on maturation and ovulation of oocytes from Rana dybowskii in vitro. Ovarian fragments or isolated follicles were cultured for 24 h in a medium containing frog pituitary homogenate (FPH) or progesterone ($P_{4}$) with or without endocrine disruptors, and oocyte maturation (germinal vesicle breakdown, GVBD) and ovulation were examined. Among the organotins, tributyltin (TBT) strongly inhibited both FPH-and $P_{4}-induced$ oocyte maturation ($ED_{50}$:0.6 and 0.7 ${\mu}M$, respectively); however, tetrabutyltin (TTBT) and dibutyltin (DBT) showed only partial suppression, while monobutyltin (MBT) showed no inhibitory effect. All of the organotins suppressed $P_{4}-induced$ oocyte ovulation very effectively at a low concentration, and TBT and DBT exerted an inhibitory effect on FPH-induced ovulation. Among the heavy metals, mercury (Hg), cadmium (Cd) and cobalt (Co) were very effective in inhibiting FPH-induced oocyte maturation and ovulation, while lead (Pb), arsenite (As) and zinc (Zn) were less effective. However, all of the heavy metals suppressed FPH-induced oocyte ovulation at a high dose ($100{\mu}M$). Among the azoles, itraconazole (ICZ), ketoconazole (KCZ) and clotrimazole (CTZ) effectively inhibited FPH-induced oocyte maturation and ovulation, while econazole (ECZ), miconazole (MCZ) and fluconazole (FCZ) were considerably less effective. These results demonstrated that the abovementioned endocrine disruptors exhibited differential effects on oocyte maturation and ovulation in amphibian follicles and that the frog ovarian culture system could be used as an effective experimental tool to screen and evaluate the toxicity of various endocrine disruptors in vitro.

• 분석과학
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• 제14권2호
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• pp.115-122
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• 2001

우리나라 해안에 인접한 "K"지역 병원에서 구한 44명의 혈액에서 유기주석화합물인 mono-butyltin(MBT), dibutyltin(DBT) 그리고 tributyltin(TBT)을 불꽃광도검출기가 부착한 가스크로마토그라프로 분석하였다. 본 연구의 목적은 일부 주민의 혈액을 대상으로 MBT, DBT, TBT에 대한 분석방법과 농도를 고찰하는 것이다. 본 연구에서 이용한 분석방법에 대한 검출한계(method detection limit, MDL)는 MBT 3.67, DBT 0.91, TBT는 1.09ng Sn/g 습중량 기준으로 나타났다. 또한 일본 국립환경연구소가 제조한 농어중의 $1.3{\mu}g/g$ TBT as chloride의 농도가 가진 표준물질(standard reference material)을 분석한 결과 공인값과 잘 일치하였다. 혈액 중에서 검출된 농도의 범위는 MBT가 3.69-7.93ng Sn/g, DBT 1.15-5.41ng Sn/g이었고, TBT는 검출한계 미만 및 미검출이었다. 혈액중에서 검출된 MBT 및 DBT의 흡수와 축적은 사람들이 유기주석화합물이 생체축적된 수산물의 섭취, 각종 플라스틱류 사용 등에 원인이 있을 것으로 사료된다. 혈액중 유기주석화합물이 인체로 흡수되는 내재용량(internal dose)을 평가할 수 있는 지표서의 신뢰성에 관한 연구가 계속해서 진행되어야 할 것으로 판단된다.

• 한국산학기술학회논문지
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• 제18권1호
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• pp.216-221
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• 2017

폴리머 안경렌즈를 제조할 때 가시광선 영역에서 투과되는 빛을 증가시키고, 안경렌즈 표면에 형성되는 허상을 방지하는 반사방지 기능은 매우 중요하다. 본 연구에서는 굴절률 1.56, 1.60 및 1.67을 갖는 안경렌즈를 폴리머 렌즈 모노머 및 이염화 이부틸 주석 촉매제, 알킬 인산 에스터 이형제 등의 혼합물을 인젝션 몰드 방법으로 열중합 공정을 적용하여 제조하였다. 폴리머 안경렌즈 표면에서의 반사방지 효과를 조사하기 위하여 다층 박막 반사방지 코팅 구조(양면 또는 단면 코팅), 3층 박막의 Gaussian gradient-index profile 불연속 근사 반사방지 코팅 구조, 3층 박막의 quarter-wavelength 근사 반사방지코팅 구조 등 다양한 반사방지 코팅 구조를 설계하였고, E-beam 증착 시스템을 이용하여 열중합공정으로 제조된 폴리머 안경렌즈에 각각 코팅하였다. 폴리머 안경렌즈의 광학적 특성은 UV-visible spectrometer로 분석하였다. 반사방지 코팅 층을 구성하는 박막의 굴절률, 표면 거칠기 등의 소재 특성은 Ellipsometer와 원자힘 현미경(AFM)으로 분석하였다. 분석결과, 굴절률 1.56의 낮은 굴절률을 갖는 폴리머 안경렌즈에서 가장 효과적인 반사방지 코팅 구조는 다층 박막 반사방지 코팅 구조의 양면코팅이었다. 하지만 굴절률 1.67의 고굴절률 안경렌즈에 대해서는 3층 박막의 Gaussian gradient-index profile 불연속 근사반사방지 코팅 구조의 양면 코팅도 다층박막 반사방지 코팅구조의 양면코팅에 상응하는 반사방지 효과를 나타내었다.

• 폴리머
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• 제27권5호
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• pp.470-476
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• 2003

고굴절률을 갖는 플라스틱 재료를 얻기 위하여 1,2-에틸렌디설파닐비스(2-머캅토메틸-1-에탄티올) (ESTT)을 1,2-에틸렌디설파닐비스(2-브로모메틸-1-에탄티올) (ESTB)과 티오우레아의 반응과 암모니아 용액으로 가수분해 반응을 해서 높은 수율로 새로이 합성하였고, $^1$H-NMR, $^{13}$C-NMR, FT-IR및 Mass Specooscopy 등에 의해 1.7 ppm에서 -SH, 28.4 ppm에서 -CH$_2$SH, 2540 $cm^{-1}$ /에서 -SH등의 관능기 구조를 확인하였다. 이어서, 폴리티오우레탄 (PTU)들은 디부틸틴 디라울레이트 존재하에서 ESTT와 4,4＇-메틸렌비스(페놀이소시아네이트) (MDI), 톨릴렌 2,4-디이소시아네이트 (TDI), 이소포론 디이소시아네이트 (IPDI), m-자일렌디이소시아네이트 (XDI) 및 1,6-디이소시아네이토헥산 (HMDI) 등을 일정한 틀에 넣고 주형중합을 하고, FT-IR로 N=C=O의 존재를 확인하였다. 이어서, PTU 수지들의 열적, 기계적 및 광학적 성질을 살펴보기 위하여 열주사분석 (DSC)과 열중량분석 (TGA), 경도 및 굴절률 측정 등을 행하여, PTU 시편들이 DSC상에서 융점이 없고 XRD상으로 무정형임을 관찰하였다. 또, 110 $^{\circ}C$ 이상의 유리 전이 온도를 갖는 PTU 수지들은 86∼89 범위의 양호한 경도 (Shore D)를 나타냈으며, 방향족 고리를 함유하는 디이소시아네이트와 ESTT를 원료로 했던 PTU수지들의 내열성이 특별히 양호하였다. 무정형 PTU 수지들은 400∼600 m 범위의 UV-vis 광원에 의한 광투과율 들도 양호하게 나타났다. PTU 수지들은 1.60 이상의 굴절률을 보였으며, 황함량이 증가하면 굴절률도 점차 증가하는 것이 관찰되었다.