Earticle

Halogen compounds refer to compounds formed by the combination of halogen elements - Fluorine(F), Chlorine(Cl), Bromine(Br), Iodine(I) - with other elements. Industrial uses of halogen compounds include pharmaceuticals, pesticides, plastics, cleaning agents, flame retardants, as well as well-known fire extinguishing agents like halon and clean fire extinguishing agents. However, despite the wide range of products and applications of these halogen compounds, there is limited knowledge regarding their physical hazards. This is related to the health hazards and environmental hazards associated with halogen compounds as well. Halogen compounds are known to be health hazard substances that, depending on the type, can cause toxicity, carcinogenicity as well as endocrine disruptors. In addition, depending on the type, some halogen compounds are known as environmental hazards that contribute to ozone layer depletion and global warming attribution. Halogen compounds are used as fire extinguishing agents and flame retardants, and due to their recognition as substances with health hazards and environmental hazards, physical hazards are often overlooked. However, depending on the type, some halogen compounds can pose hazards such as highly flammable gases or special flammable liquids. This study aims to distinguish the contrasting properties of halogen compounds, such as their flame retardant and fire extinguishing characteristics versus their flammability from an organic chemical structural perspective. The conclusions of this study will serve as foundational data for investigating the flammability risks of halogen compounds in fire investigations.

본 연구의 제1보에 뒤이어서 방향족 염소유도체외 Szilard Chalmer 반응으로 얻어진 유기충치 성분을 분리하여서 표지 조건을 검토하였다. 여러가지 성분을 모두 분리할 수는 없었으나 주성분을 증류법 및 박층 Chromatography등으로 분리하였으며 그 화학구조가 원시료의 표지물임을 확인하였다. 고체시료의 경우에는 주성분이 유기표지물의 80-60%이였고 액체시료에 있어서는 70% 이하였다. 장시간 조사하면 주성분 수율이 증가되었으나 방사선에 불안정한 화합물의 경우에는 도리어 감소하였다. Chromatography로 분리되는 부생성물들의 수율은 액체시료의 경우 많았으나 고체의 경우는 이 보다 적었고 따라서 주생성물의 분리가 용이하였다. 각 화합물의 표지수율을 표시하고 Chromatography에 의한 분리조건을 논의하였으며 이 표지 방식의 실용성을 화학구조와 관련시켜 고찰하였다.

In a continuation of the 1st series of these studies, a separation of the components in organic phases obtained from Szilard Chalmer reactions of aromatic chloro derivatives was attempted to clarify the conditions of isolating the main component. Though it was unable to isolate all constituents of organic phases, the main component was well isolated by means of a simple distillation or a thin layer chromatography. It was identified that the main component was a recombined product of the recoiled $^{38}$ Cl atom with the original sample. In cases of solid samples the main component amounted about 80-60% of the radio activity of the organic phase, whereas the main component from liquid samples gave less than 70% of the radio activity of the organic phase. A prolonged irradiation could increase the yield of a main component, but it was, in case of a radiation senintive compound, decreased as the irradiation is extended. The number of aide produets separated from an organic phase of a liquid sample was greater than that of a solid sample, and hence the main component of a solid sample was isolated easier. The overall fields of the labelled main products of 22 kinds of compounds were listed and a procedure of the separation of the main component by a thin layer chromatograply was proposed and evaluated. The feasibility of the present procedure for labelling purpose was also reviewed with respects to the chemical structure of a compound.

A quantitative analysis method of halogen elements in volatile organohalogen compounds was established by the Wickbold combustion pretreatment in an enclosed system and ion chromatography. The sample pretreatment parameters of Wickbold combustion were experimentally optimized, and using the determined optimal pretreatment parameters, the reproducibility was estimated by ion chromatography. As a comparison for real samples, NIST certified reference materials (CRMs) were analyzed for the recovery efficiency and reproducibility.

${\alpha},{\beta$}-dichloro-${\beta$}-phenyl propionate, Ethyl ${\alpha},{\beta$}-dibromo-${\beta$}-phenyl propionate, Etyyl ${\alpha},{\beta$}-dichloro-${\beta$}-(p-chlorophenyl)propionate, 및 dibromo-styrene 等의 化合物을 各種溶媒(dimethly formamide, diethylene glycol, 및 diethylene glyco monomethyl ether 等) 存在下에서 弗化反應을 시켜 보았으며 放射性弗素-18을 追跡子로 使用하여서 위의 化合物들의 弗化카리에 對한 反應度를 檢査하여 보았다. 一般的으로 弗化反應 生成物은 모노弗化物과 脫할로겐된 二重結合物을 生成하였다. diethylglycol 存在下에서 高溫反應시킨 條件下에서는 二重結合生成物이 많았고 diethylene glyco-monoethyl ether 存在下에서 低溫反應시킨 條件下에서는 弗化物이 多量生成하였다. 모노弗化物의 合成方式 및 確認方法에 關하여 說明하였으며 本反應의 合成上의 用途($F^{18}$ 標識化合物包含)에 言及하였다.

Flourination of Ethyl, ${\alpha},{\beta$}-dichloro-${\beta$}-phenyl propionate, Ethyl ${\alpha},{\beta$}-dibromo ${\beta$}-phenyl propionate, Ethyl ${\alpha},{\beta$}-dichloro ${\beta$}-(p-chloro-phenyl) propionate, and dibromostyrene by potassium fluoride were investigated in presence of dimethyl formamide, diethylene glycol, and diethylene glycol monomethyl-ether. The reactivity of these organic halogen esters and hydrocarbons towards potassium fluoride was checked further by means of radioactive fluorine-18. tracer. Generally, the reaction gave monofluoride together with dehalogenated olefin. The formation of olefine was increased when the reaction was done at high reaction temperature in presence of diethylene glycol, whereas the lower reaction temperature in presence of diethyleneglycol monomethyl ether favored the formation of mono fluoride in a good yield. The procedures and methods of the identification of monofluorides were described and the feasibility of this reaction of fluorine containing ester including the F-18 labelled compounds was discussed.

토루엔, 디메틸폴움아마이드, 디메틸슬포옥사이드, 테트라하이드로퓨란, 아세토나이트라일 및 디옥센 等 溶媒存在下에서 모노클로로醋酸과 亞鉛을 反應시켜 본 結果, 溶媒효果를 나타내었다. 反應試藥의 反應度가 溶媒의 極性 및 親水性에 따라 增加하였다. 같은 溶媒系를 使用하여 에틸모노클로로醋酸을 反應시켜 본 結果, 溶媒효果를 나타냈으나 酸의 境遇보다 그 差가 크지 못하였다. 酸, 에스타, 亞鉛 및 카보닐化合物(벤즈알데히드 및 4-헤프타논)의 反應에 있어서는 알데하이드의 境遇에 있어서는 Reformatsky 反應生成物을 주었으나, 4-헤프타논과의 反應度는 없었다. 反應生成物의 收率은 試藥添加方法에 따라 變化되었다. 最高收率은 酸의 하이드로옥시酸(38.5%), 0.8g의 salt(아세트나이트라일溶媒)이며, 에스타의 境遇에는 에틸신나메이트(19.3%), 폴리머(21.6%)이였다. 카보닐化合物의 境遇에 있어서는 反應溫度에 따라 試藥의 反應度의 變化가 있었다. 硏究結果를 溶媒效果에 關聯시켜 論議하였으며, 硏究方法에 關하여 記述하였다.

Reaction of monochloroacetic acid with zinc in presence of toluene, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, and dioxane solvents showed the solvent effect in order of dimethylformamide, dioxane, dimethyl sulfoxide, toluene, acetonitrile, and tetrahydrofuran. The increasing reactivity of the reagents was observed in order of the polarity and hydrophilicity of the solvent. The same reaction of ethyl monochloroacetate in the same series of solvents showed also the solvent effect, but the difference was not large as compared to that of the acid. The reaction of the acid, ester, zinc, and carbonyl precursors such as benzaldehyde and 4-heptanone gave the Reformatsky reaction product in the case of the aldehyde, but the reactivity with 4-heptanone was slight. The yield of the product was varied by the method of addition of reagents. The best yield observed in case of the acid reaction was 38.5% of the hydroxy acid and 0.8g of the salt in presence of acetonitrile and in case of the ester reaction 19.3% of ethyl cinnamate and 21.6% of polymer. The variation of the reactivity of reagents due to the reaction temperature was observed in case of carbonyl reaction. The result was discussed in terms of the solvent effect and the procedures were described.

有機含鹽素 에스테르, 알콜, 및 산과 金屬亞鉛 및 錫을 dimethyl formanmide 溶媒存在下에서 反應시킨 結果 有機金屬 콤프렉스를 좋은 收率로 生成하였다. 같은 反應을 混合紫外線照射下에서 進行시킨 結果 高溫 以外에서는 콤프렉스의 生成이 크지못하였다. D.M.F.에 依한 金屬 콤프렉스의 溶解效果는 토루엘이나 사이크로헥산보다 훨씬 컸었다. 鹽素를 含有한 酸에서는 酸의 金屬鹽의 金屬 콤프렉스가 生成됨을 觀察하였다. 카보닐 precursor와의 反應에 있어서는 少量의 雙合物과 함께 附加物을 生成하였으나 收率이 높지 못하였다(산 30∼40%, 에스테르 73%, 알콜 14.6%). 그러나 이 方法은 從來法에 比하여 簡便한 것임을 알았다. 硏究結果를 溶媒效果에 關聯시켜 論議하였으며 實驗方式을 報告하였다.

Reaction of organic chlorine containing ester, alcohol, and acids with metallic tin and zinc in dimethyl formamide solvent gave a good yield of organo metallic complex. The same reaction under a mixed U.V. irradiation could not give an appreciable yield of the complex except in the case of an elevated reaction temperature. The solvation effect of dimethyl formamide of the metallic complex formation was markedetly increased as compared to the reaction in toluene and cyclohexane. In case of chlorine containing carboxylic acid, the formation of organo chloro zinc complex of the salt was observed. The reaction of organo zinc complex with a carbonyl precursor gave the addition product together with a dimerized product. Especially the aldehyde species enhanced the formation of zinc complex. The addition reaction was simple and convenient, but the yield was not high.(30-40% for the acid, 73% for the ester, 14.6% for alcohol). The result was discussed on basis of solvent effect and the procedures were described.

<디메칠호롬아마이드> 溶媒系에서 有機含할로겐化合物을 弗化加里와 反應시켜 본 結果 $CF_3COOH,\;C_3F_7COOH,\;C_2F_5COOH$와 같은 含弗素有機酸에서는 脫炭酸反應이 일어나며, 含鹽素有機酸, $CH_2ClCOOH,\; CH_3CHClCOOH,\;CHCl_2COOH $및 $o-Cl-C_6H_4COOH$은 一部 弗化反應이 일어나고 雙合(dimerization) 反應이 隨伴된다는 것을 究明하였다. 芳香族할라이드類에서는 反應度를 나타내지 않았으나 芳香環에 誘電子置換基가 두個있는 試藥에서는 主로 雙合反應을 일으켰다. 알콜 및 에스테르類는 通常的인 弗化反應을 잘 일으켰다. 같은 反應을 溶媒 使用치 않고 高溫에서 進行시켜 본 結果 雙合反應物의 收率을 增加시켰고 $o-ClC_6H_4COOH$에서는 環化物(fluorenone)을 少量生成하였다. 反應段階中의 各 試藥의 消耗및 生成에 對한 化學量的關系를 比較檢討한 結果 酸의 反應에서는 普通 脫炭酸反應보다 弗化反應이 優先 進行됨을 究明하였다. 弗化加里의 反應觸發作用및 反應機構에 關하여서는 論議하였다.

Reactions between potassium fluoride with organic halogen-containing carboxylic acids in dimethyl formamide solvent gave a decarboxylation reaction for the case of fluoro carboxylic acids of the type of $CF_3\;COOH,\;C_3F_7COOH,\;and\;C_2F_5COOH,$ whereas an additional partial fluorination together with dimerization reaction occurred for the chlorine containing acids of the type of $CH_2ClCOOH,\;CH_3CHClCOOH, \;CHCl_2COOH\;and\;o-Cl-C_6H_4-COOH.$ The phenyl halides showed no reactivity, but the halides with two electron attracting substituents on the benzene ring gave mainly dimerization reaction. The esters and alcohols gave an usual fluorination reaction. The same reactions in absence of the solvent at the elevated temperature increase the yield of the dimerized product and gave the cyclized product, fluorenone, in case of ο-chlorobenzoic acid. It was found that the fluorination usually precede the decarboxylation reaction by checking the stiochemical sequence of reaction. Catalytic influence of potassium fluoride were discussed and the mechanism of the reaction was considered.

展開한 페이퍼크로마토그램을 韓國 Triga-Mark-Ⅱ 硏究用 原子爐의 뉴마딕튜부施設(中性子線束; 1.5{\times}$10^{12}n/cm^2$, sec)을 利用하여 照射하여 본 結果 크로마토그램上에 展開된 스폿트(spot)를 定性的으로 確認할 수 있었다. 有機하로겐 化合物(크로로酸, 크로로에스테르, 沃化物, 及 弗化物)에 있어서 一般發色法으로서는 明確한 着色스폿트(spot)를 나타내지 못한 것에 있어서도, 이 方法으로서 展開된 스폿트를 明確히 區別할 수 있었다. 濾紙成分의 放射化에 依한 誤差를 減少시키기 爲하여 濾紙두께 補正 及 放射化度 補正을 硏究한 結果, 濾紙두께 補正 及 放射能崩壞 補正法을 究明하였으며, 이 方法으로 스폿트를 放射化하여 定性分析하는데 좋은 結果를 얻을 수 있었다. 有機하로겐化合物의 分析 及 確認에 있어서의 이 方法의 效用性에 關하여 論議하였다. 濾紙相으로는 正常相 及 逆相을 함께 使用하였다.

When a developed paper partition chromatogram was irradiated by means of the pneumatic tube system of the Korean research reactor (neutron flux: 1.5 ${\times}10^{12}n/cm^2$sec.) the qualitative confirmation of the developed spot on the chromatogram was possible. In the case of an organic halogen compounds (chloro-acid, chloro-ester, iodide, and fluoride) the spot analysis was possible by the present method whereas the same spot could not give the distinct coloring with a common coloring reagents. Filterpaper thickness calibration and activity calibration induced by irradiation of the components of the filter paper, which were a source of erraneous interpretation of the spot, were searched and an average filterpaper calibration method and filter paper activity were improvised to obtain a good qualitative analysis of the spot. Finally the use and applicability of this method for the analysis identification of an organic halogen compound were evaluated. As the filter paper phase an ordinary phase (Whatmann #1, filter paper) and reversed phase (liquid paraffin impregnated) were used.

In this study, some materials are organized and experimented with variables to obtain the optimum mix proportion for the mechanical property of halogen free flame resistance compound with varying addition of nano clay. Tensile strength, density and stiffness are tested in the room temperature. In this study, unlike existing layered structure, nano clay with tabular structure is used and sufficient stiffness, strength, thermal stability and gas block capability can be achieved with small amount of addition. Tensile strength and elongation test show high rupture strength only in specimens with compatibilizing agents while density test shows average measurement in all the specimens except T-9. It was confirmed that the measurement value according to the additives in compatibilizing agent or in nano clay of hardness test represents similarly.

The object of this study is to obtain the optimum mix proportion of halogen free compound with flame resistance and, for the purpose, thermal/electrical characteristics test are conducted using compatibilizing agents, flame resistance agents, hydroxide aluminum, sunscreen, antioxidant and silicon oil on the base resin of linear low density polyethylene (LLDPE), Ethylene vinyl acetate copolymer (EVA). Existing compound method accompanies many requirements to be satisfied including a lot of addition of flame resistance agents, prohibition of impact on mixing capability with base and property and etc. In this study, different from the existing method, the optimum mix proportion is determined and experimented by adding nano clay. Oxygen index test shows no difference between specimens while T-6, T-9 shows oxygen index of 29[%] and 26[%], respectively. This is concluded that hydroxide aluminum, which is a flame resistance agent, leads low oxygen index. From UL94-V vertical flame resistance test, the combustion behavior is determined as V-0, Fail based on UL94-V decision criteria. Viscometry shows low measurements in specimens with separate addition of compatibilizing agents or nano clay. Volume resistivity test shows low measurement mainly in specimens without compatibilizing agents. Therefore, with the flame resistance compound shows better performance for thermal/electrical property and the optimum mix proportion are achieved among many existing materials.