• 한국환경보건학회지
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• 제39권5호
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• pp.408-417
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• 2013

Objectives: Phthalates are used as plasticizers in polyvinyl chloride (PVC) plastics. As phthalate plasticizers are not chemically bound to the PVC, they can leach, migrate or evaporate into indoor air and atmosphere, foodstuffs, other materials, etc. Therefore, humans are exposed through ingestion, inhalation, and dermal exposure over their entire lifetime, including during intrauterine development. In particular, university students have a great number of opportunities to contact products including phthalates during campus life (food packaging, body care products, cosmetic, lotions, aftershave, perfume etc.). The purpose of this study was to examine levels of phthalate exposure as undergraduate students begin to use pharmaceuticals and personal care products including phthalates. Methods: Phthalate metabolites, mono-ethyl phthalate (MEP), mono-n-butyl phthalate (MnBP), mono-isobutyl phthalate (MiBP), mono-2- ethylhexyl phthalate (MEHP), {(mono-(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP}, and mono-(2-ethlyl-5-oxohexyl) phthalate (MEOHP} were examined. 80 urine samples collected from university students were analyzed using LC/MS/MS(API 4000, Applied Bioscience) with on-line enrichment and columnswitching techniques. This study was carried out at Y university located in Gyonggi Province from 2008 to 2011. Results: The detection limit of phthalate metabolites were 0.03 ng/mL for MEP, 0.11 ng/mL for MnBP, 0.08 ng/mL for MiBP, 0.93 ng/mL for MEHP, 0.19 ng/mL for MEOHP and 0.16ng/mL for MEHHP. MnBP showed the highest urinary levels (median: 31.6 ug/L, 24.8 ug/g creatinine (cr)). Concentrations were also high for MEHHP (median: 24.1 ug/L, 19.0 ug/g cr), followed by MEOHP (median: 22.8 ug/L, 17.9 ug/g cr). In individual cases, the maximum level reached up to 348 ug/L, and 291 ug/g cr, respectively. The urinary and creatinine adjusted levels of MEP were lower than those for DBP and DEHP metabolites, but were higher in 95th percentiles. As a result, the mean daily DEP intake value was 2.3 ${\mu}g/kg$ bw/day, 3.5 ${\mu}g/kg$ bw/day for DEHP and 4.9 ${\mu}g/kg$ bw/day for DBP. Conclusion: These students' phthalate exposure levels were below the international safe level set by the EU, but higher than the 2012 KFDA survey of the age group from 3 to 18.

• 한국발생생물학회지:발생과생식
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• 제24권1호
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• pp.1-17
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• 2020

Phthalates and those metabolites have long history in industry and suspected to have deficient effects in development and reproduction. These are well-known anti-androgenic chemicals and many studies have examined the effects of these compounds on male reproduction as toxins and endocrine disruptors. Uterus is a key organ for proper embryo development, successful reproduction, and health of eutherian mammals including women. To understand the effects of the phthalate, the horizontal approach with a whole group of phthalate is best but the known phthalates are huge and all is not uncovered. Di-(2-ethylhexyl) phthalate (DEHP) is the most common product of plasticizers in polymer products and studied many groups. Although, there is limited studies on the effects of phthalates on the female, a few studies have proved the endocrine disrupting characters of DEHP or phthalate mixture in female. An acute and high dose of DEHP has adverse effects on uterine histological characters. Recently, it has been revealed that a chronical low-dose exposing of DEHP works as endocrine disrupting chemicals (EDC). DEHP can induce various cellular responses including the expression regulation of steroid hormone receptors, transcription factors, and paracrine factors. Interestingly, the response of uterus to DEHP is not monotonous and the exposed female has various phenotypes in fertility. These suggest that the exposing of DEHP may causes of histological modification in uterus and of disease in female such as endometriosis, hyperplasia, and myoma in addition to developmental and reproductive toxicity.

• 한국산업보건학회지
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• 제24권3호
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• pp.365-370
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• 2014

Objectives: The major objective is development of an eco-friendly non-phthalate plasticizer using crude glycol derived from the biodiesel process. Methods: Glycerol monolaurate(GML) was synthesized from glycol and triglyrcerides. Glycerol diacetomonolaurate(GDAL) was synthesized from GML and acetic acid. Results: The synthesis of the GDAL plasticizer was measured with nuclear magnetic resonance spectroscopy(NMR). Mechanical properties were measured by universal testing machine(UTM) and the experimental values were compared with phthalate plasticizers such as dioctyl phthalate(DOP). In particular, the values for tensile strength and elongations with GDAL were higher than with DOP. Conclusions: We confirmed the development of an eco-friendly non-phthalate plasticizer by NMR. Based on our results, applicability for food and drug packaging materials was found.

• 한국입자에어로졸학회지
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• 제6권1호
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• pp.1-7
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• 2010

Generally, large amounts of DOP(Di-Octyl Phthalate) chemicals are used as plasticizers in PVC compound manufacturing processes. However, it is very important to collect DOP species immediately from a workplace in order to protect worker's heath and recover them. To accomplish these objectives, we need to understand the droplet formation and growth mechanisms of DOP species. In this study, two important parameters such as temperature gradient and residence time were considered to clarify these mechanisms. We found that residence time is very critical to determine the droplet size distribution of DOP, whereas temperature gradient in general operating conditions(less than $-6.8^{\circ}C/cm$) is negligible.

• Composites Research
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• 제35권4호
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• pp.232-241
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• 2022

가소제는 가공성 및 연성과 같은 기계적 특성에 바람직한 영향을 미치기 위해 중합체에 첨가되는 화학 첨가제이다. 본 논문에서는 플라스틱 시장에서 전통적으로 사용되어온 프탈레이트 기반 가소제를 대체할 수 있는 친환경 가소제의 사용과 시장에 대해 탐구한다. 바이오 가소제는 주로 농산물, 부산물 및 폐기물을 포함하는 바이오 매스 소스에서 파생된다. 바이오 매스 공급원과 관계없이 이상적인 친환경 가소제는 무독성이며, 휘발·추출·이행 현상에 대한 저항성이 높고, 상용성과 혼화성이 좋으며, 경제적이어야 한다. 글로벌 바이오 가소제 시장은 2020년 13억 달러에서 2030년까지 21억 달러에 이를 것으로 전망되며, 2021년에서 2030년까지 5.31% CAGR로 성장할 것으로 예상된다.

• Toxicological Research
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• 제27권4호
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• pp.191-203
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• 2011

There has been growing concern about the toxicity of phthalate esters. Phthalate esters are being used widely for the production of perfume, nail varnish, hairsprays and other personal/cosmetic uses. Recently, exposure to phthalates has been assessed by analyzing urine for their metabolites. The parent phthalate is rapidly metabolized to its monoester (the active metabolite) and also glucuronidated, then excreted. The objective of this study is to evaluate the toxicity of phthalic acid (PA), which is the final common metabolic form of phthalic acid esters (PAEs). The individual PA isomers are extensively employed in the synthesis of synthetic agents, for example isophthalic acid (IPA), and terephthalic acid (TPA), which have very broad applications in the preparation of phthalate ester plasticizers and components of polyester fiber, film and fabricated items. There is a broad potential for exposure by industrial workers during the manufacturing process and by the general public (via vehicle exhausts, consumer products, etc). This review suggests that PA shows in vitro and in vivo toxicity (mutagenicity, developmental toxicity, reproductive toxicity, etc.). In addition, PA seems to be a useful biomarker for multiple exposure to PAEs in humans.

• Bulletin of the Korean Chemical Society
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• 제29권1호
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• pp.165-167
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• 2008

The performances of tetracycline based cation selective polymeric membrane electrodes of many sets with different plasticizers were investigated as the selectivity of ion-selective electrodes and optodes are greatly influenced by membrane solvent and also controlled by plasticizers. The membrane 1 with Bis(2-ethylhexyl) sebacate (DOS) and additive shows good potentiometric performance toward Ca2+ (slope: 27.8 mV per decade; DL: -4.52) including selectivity. Contrastingly, membrane 4 with Dibutyl phthalate (DBP) shows near-Nernstian response, it has also shown the best measuring range and detection limit for Ca2+ (29.5 mV and -5.10) and Mg2+ (24.4 mV and -5.04) and the least selectivity has been also observed between Ca2+ and Mg2+. When the membrane 1 and 4 were used together to flow system, we could determine the concentration of Ca2+ and Mg2+, simultaneously.

• 공업화학
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• 제34권3호
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• pp.252-257
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• 2023

본 연구에서는 내분비계 교란 물질로 알려진 프탈레이트계 가소제를 대체하기 위하여 동·식물성 오일로부터 추출되는 지방산과 고리를 포함하는 알코올을 이용하여 가소제 후보물질을 합성하고, 가소화 효율을 포함한 가소제로서의 특성을 평가하였다. 지방산 3종(caprylic acid, capric acid, lauric acid)과 알코올 3종(solketal, benzyl alcohol, cyclohexanol)의 에스터화 반응으로 합성한 9종의 화합물의 구조는 ¹H-NMR을 이용하여 확인하였다. 합성한 9종의 가소제 후보물질은 PVC 수지에 첨가하여 가소 특성을 평가하였고, 상용 가소제인 di-2-ethylhexyl phthalate (DEHP), di(isononyl)cyclohexane-1,2-dicarboxylates (DINCH), epoxidized soybean oil (ESO)과 비교·분석하여 대체 가소제로서의 가능성을 평가하였다. 결과에 따르면 가소화 효율은 DEHP 대비 0.96~1.02 배, ESO 대비 0.94~0.98 배로 비슷한 결과를 얻었으며, DINCH의 경우보다는 1.05~1.10 배 우수한 결과를 보였다. 열적 안정성은 DEHP, DINCH보다 다소 떨어지나 ESO의 경우보다는 우수한 결과를 나타내었다. 용출성 시험 결과, 수성용매인 물과 유성용매인 노말 헥세인에서 DEHP, DINCH보다 다소 높은 결과를 보였으나 ESO 대비 유사하거나 우수한 특성을 나타내는 것을 확인하였다.

• 공업화학
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• 제28권1호
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• pp.42-49
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• 2017

프탈레이트계 PVC 가소제를 대체하기 위해 식물유 기반 아세틸화 모노글리세라이드(AMG)계 가소제를 합성하여 PVC에 대한 가소성능을 평가하였다. 코코넛 오일과 글리세롤로부터 전이 에스테르화 반응과 아세틸화 반응을 거쳐 AMG-CoCo를 합성하였고 글리세롤 모노올리에이트(GMO)로부터 아세틸화 반응을 통해 AMG-GMO를 그리고 추가적으로 에폭시화 반응을 거쳐 AMG-GMO-Epoxy 합성하고 그 구조들을 확인하였다. AMG계 가소제의 열안정성을 평가한 결과, AMG-CoCo < AMG-GMO < AMG-GMO-Epoxy 순으로 열분해 온도가 높았으며 모두 상용 가소제인 DOP의 열분해 온도보다 높았다. AMG계 가소제를 함유한 PVC의 경우, 인장 신율은 770~810%, 인장 강도는 약 19~22 MPa로 DOP로 가소화된 PVC보다 우수하였다. DMA 분석 결과, AMG-GMO-Epoxy와 PVC는 매우 우수한 섞임성을 보여주었고 AMG-GMO-Epoxy를 50 phr 함유한 PVC의 $T_g$는 $24^{\circ}C$까지 감소하였다. 물에 대한 가소제의 용출 실험 결과, AMG-GMO와 AMG-GMO-Epoxy를 50 phr 포함한 PVC 경우 무게 감소가 약 2%와 1%로 내용출성이 매우 우수함을 알 수 있었다. 따라서 AMG-GMO-Epoxy가 DOP를 대체할 PVC 가소제로 경쟁력이 있다고 할 수 있다.

• 한국환경보건학회지
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• 제34권4호
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• pp.271-278
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• 2008

Dialkylated phthalates have been commonly used as plasticizers and a variety of applications. Phthalate diesters have been shown to be developmental and reproductive toxicants. It is very difficult to exactly estimate the dose of dialkylated phthalates taken up by the general population because of environmental contamination. Urinary metabolites of phthalates enabled to estimate internal exposure. The objective of this study was quantitative determination of phthalate metabolites by LC/MS/MS with on-line cleanup method to analyze phthalate metabolites in Korean children's urine. We employed LC/MS/MS with on-line enrichment and column-switching techniques for this biological monitoring. Metabolites determined were 4 primary metabolites; MEHP, MnBP, MiBP, MEP and 2 secondary metabolites of DEHP; 5-OH-MEHP), 5-oxo-MEHP. We analyzed children's urine from 30 boys and 30 girls. The method detection limit of phthalate metabolites were 0.03 ng/mL for MEP, 1.05 ng/mL for MBP, 0.22 ng/mL for MEHP, 0.15 ng/mL for 5-OHMEHP and 0.16 ng/mL for 5-oxo-MEHP, respectively. Switching Column LC/MS/MS was proven to be a useful tool to determine metabolites of phthalate diesters in human urine. The correlation among phthalate metabolites was very high and statistically significant, except MEP. The children's age (months) was negatively correlated to the concentration of phthalate metabolites. The geometric mean concentration of phthalate metabolites (mg/g creatinine) in children's urine were 25.5 for MEP, 130.3 for MnBP, 56.8 for MiBP, 19.5 for MEHP, 85.6 for 5-OH-MEHP and 83.1 for 5-oxo-MEHP, respectively. Levels of estimated daily intake of parent phthalate compounds (${\mu}g$/kg bw/day) were 0.8 for DEP, 5.0 for DnBP, 1.9 for DiBP and $8.9{\sim}14.2$ for DEHP, respectively. Estimated daily intake for DEP and DiBP were lower than those of other studies but the value for DEHP was higher than that of other study.