金屬이온結合性 高分子킬레이트에 關한 硏究

최규석,신세건,최길현,김문걸,Kyu Suck Choi,Sae Kun Shin,Kil Hyun Choi,Mun Kul Kim 대한화학회 1977 대한화학회지 Vol.21 No.1

m-Phenylenediamine(以下 MPD로 略함)과 resorcinol(以下 RES로 略함)을 몰比를 달리하면서 포름알데히드와 酸化觸媒 존재하에서 反應시켜 生成되는 附加共縮合型 樹脂를 流動파라핀을 사용하여 서스펜젼重合시켜 60∼80 mesh의 粒狀重合體를 合成하고 이를 精製한후 5, 10, 15, 20, $25{\%}$의 水酸化 나트륨 水溶液으로 처리한후, 原樹脂와 이들 알칼리 處理樹脂의 金屬이온들에 대한 吸着性을 檢討하였다. $Cd^{2+}$이온에 대한 흡착성은 原樹脂보다 水酸化나트륨水溶液을 처리한 경우 현저히 吸着性은 向上되지만 MPD : RES의 몰比 가 增加함에 따라 原樹脂의 경우와는 달리 減少하는 경향을 나타내며 $Pb^{2+}와\;Al^{3+}$이온들은 알칼리처리로 吸着能增加와 더불어 MPD : RES의 몰比가 2 : 1에서 最大値를 나타내며 $Ca^{2+}$이온의 경우는 MPD : RES의 몰比가 1 : 1에서 최대치를 나타내고 있다. $Mg^{2+}과\;Co^{2+}$이온들은 거의 類似한 傾向을 나타내어 MPD : RES의 몰比增加와 더불어 吸着能은 減少하는 傾向을 나타낸다. $Hg^{2+}$이온의 경우는 特異하며 MPD : RES의 몰比가 減少함에 따라 吸着能은 현저히 增加하는 경향을 나타내어 窒素含宥킬레이트와의 結合性이 强한 一般性과 잘 一致하고 있다. 이 系의 樹脂들은 輕金屬 이온(例 $Ca^{2+},\;Mg^{2+}$) 들보다 重金屬이온(例 $Cd^{2+},\;Hg^{2+}$)들에 對한 吸着力이 현저히 優秀하다. In the addition condensation reaction of m-phenylenediamine(MPD) and resorcinol (RES) with formaldehyde, the suspension polymerization in liquid paraffin was performed and the bead polymers were obtained with good results. The polymers were treated with dilute aqueous sodium hydroxide solutions in order to improve the adsorption capacity to the metallic ions and the adsorptivity to the several metallic ions, such as $Cd^{2+},\;Pb^{2+},\;Al^{3+},\;Mg^{2+},\;Co^{2+},\;and\;Hg^{2+}$ of the alkali-treated and untreated polymers were tested. These MPD-RES-F type resins showed better adsorption capacity to the heavy metallic ions such as $Cd^{2+}\;and\;Hg^{2+}$ than the light metallic ions such as $Pb^{2+},\;Al^{3+}\;and\;Mg^{2+}$, and the treatment of the resins with about 20 percent aqueous sodium hydroxide solution showed significant improvement of the adsorption capacity to the metallic ions in all cases.

金屬킬레이트化合物의 觸媒作用에 依한 Aminophenol 類의 酸化的 重縮合反應 (Ⅰ) 溶媒의 效果와 生成重合體의 特性

최규석,Choi, Kyu-Suck 대한화학회 1968 대한화학회지 Vol.12 No.3

Fe-EDTA complex, which is easily formed when Fe salt and EDTA.2Na are mixed in the aqueous medium, is found to be a very effective catalyst in the dehydropolycondensation of aminophenols. In the dehydropolycondensation of aminophenols, the catalyst, Fe(Ⅲ)-EDTA complex (higher oxidation state) is reduced to less stable Fe(Ⅱ)-EDTA complex (lower oxidation state), and the latter is easily oxidized by air to the original higher oxidation state complex, therefore the catalytic action of Fe-EDTA complex is found to be recycled effectively. Under the catalytic action of the above mentioned complex, p-aminophenol is polymerized in the aqueous medium to form the oligomers of p-aminophenol, which the degree of polymerization to be 5 or more. The oligomers formed contain partly quinone nucleus as well as amino and hydroxyl groups. In this study, the effects of the solvents and characteristics of the oligomers are discussed. These types of polymerizations catalyzed by the metallic chelate compounds are considered to be very closely related to the reactions in the living matters.

金屬킬레이트 化合物의 觸媒作用에 依한 Aminophenol 類의 酸化的 重縮合反應 (Ⅱ) Ligands 種의 效果, 混合錯物의 構造및 副反應

최규석,Choi, Kyu-Suck 대한화학회 1968 대한화학회지 Vol.12 No.3

In the oligomerization of p-aminophenol under the catalytic action of the metallic complexes, the effects of the ligands are studied. When the initial velocity of $O_2$ uptake at pH 8 using Fe(Ⅲ) as the central metal and N-hydroxylethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), 1,2-cyclohexanediaminetetraacetic acid(CyDTA) as the ligands respectively are compared, the velocities are as the following order: HEDTA > EDTA > DTPA > CyDTA. Further when the effect of the ligands, nitrilotriacetic acid (NTA), HEDTA, EDTA, and DTPA, on the yields of oligomers are compared, the result shows as the following order: NTA > HEDTA > EDTA > DTPA. These are nearly reverse order of the stability constants of the complexes. In order to determine the composition of the mixed complexes at the initial step, the method of continuous variation is used, and it is found that the composition ratio of Fe-EDTA complex to monomer in the mixed complexes is one at pH 5-8 range. It is also found that at pH 9 or in the more alkaline range, side reactions occur to form water soluble dimer of quinone type and the catalytic action of the metallic complex markedly decreases on account of the hydrolysis of the central metal by the $OH^-$ ion.

金屬킬레이트 化合物의 觸媒作用에 依한 Aminophenol 類의 酸化的 重縮合反應 (Ⅲ) 異性體의 反應, 反應機構 및 生成物의 構造

최규석,Choi, Kyu-Suck 대한화학회 1968 대한화학회지 Vol.12 No.3

In the oligomerization of p-aminophenol by the catalytic action of Fe-EDTA complex in the aqueous medium, the mixed complex intermediate, Fe-EDTA-M type, is considered to be formed, from which active radicals of the monomer are produced. In this system, polymerization is presumed to proceed as follows: Free radical formation ${\to}$ Coupling ${\to}$ Activation ${\to}$ Coupling, and so on. In this study, the form of the monomer and coordination state in the mixed complex, the catalytic action of Fe-EDTA the complex, the reaction mechanism, and the structure of the oligomers are discussed.

N-Methyl-p-Aminophenol의 酸化重合機構 및 生成重合體의 熱特性

최규석,Choi Kyu Suck 대한화학회 1972 대한화학회지 Vol.16 No.5

N-methyl-p-aminophenol은, 酸素存在下, 철-킬레이트(Fe(III)-EDTA) 水溶液中에서 酸化重合하여 黑色의 Oligo-(N-methyl-p-aminophenol)을 定量的으로 生成한다. 이 酸化重合過程에서 單量體中의 N에 結合된 $CH_3$ group이 일부 脫離되는데, 이것은 oligo-(N-methyl-p-aminophenol)을 아세톤처리하여 얻은 아세톤 可溶部와 不溶部의 赤外線스펙트럼에서 ${\delta}\;asym\;CH_3\;1460\;cm^{-1}$ 및 ${\delta}\;sym\;CH_3\;1380\;cm^{-1}$의 吸收가 候者의 경우 현저히 弱化된 것으로 明白하다. $N_2$氣流中에서 每分 $2^{\circ}C$의 上昇速度로 行한 TGA分析結果, $600^{\circ}C$에서 약 40%의 重量損傷을 나타내며, $CH_3$ 置換基가 없는 p-aminophenol보다 耐熱性이 떨어진다. 또한 이 生成올리고머의 He 氣流中에서 행한 熱分解反應에서의 生成物은 單量體인 N-methyl-p-aminophenol과 물이 確認되었고 分解가스로부터는 gas chromatography에서 $H_2,\;CO,\;CO_2$등이 確認되었다. 生成올리고머의 熱處理에서는 일부는 1次元的인 構造가 切斷되어 單量體로 分解되지만, 대부분은 melt polycondensation이 일어나 더 큰 重合體로 변함과 동시에 熱에 安定한 環式構造로 변하여 감이 確認되었다 N-Methyl-p-aminophenol was polymerized by oxidative couplng in the aqueous iron chelate solution in the presence of oxygen, and black precipitate of oligo-(N-methyl-p-aminophenol) was formed quantitatively. In this oxidative polymerization reaction, methyl group attached to N in the monomer was partly eliminated, and it was clarified by the infrared spectra from the fact that the absorption of ${\delta}\;asym\;CH_3\;1460\;cm^{-1}$ and ${\delta}\;sym\;CH_3\;1380\;cm^{-1}$ in acetone insoluble fraction was much weaker than that in acetone soluble fraction. From Thermo-gravimetric analysis, oligo-(N-methyl-p-aminophenol) showed about 40% weight loss at $600^{\circ}C$ and it was less heat-resistant than oligo (p-aminophenol) that methyl group was not contained. In pyrolysis of oligo-(N-methyl-p-aminophenol) in He atmosphere, monomer N-methyl-p-aminophenol and water were formed, and in the pyrolytic gases, $H_2,\;CO,\;CO_2$ were detected by gas chromatography. From the above facts, to the structural change on oligo-(N-methyl-p-aminophenol) when it was heat-treated, it was considered that original linear structure was partly degraded, and the most of the oligomer was to go in with melt polycondensation to form polymer, and heat-resistant cyclic structure was formed at a time.

芳香族디아민 및 아미노페놀-포름알데히드系 樹脂에 관한 硏究 (第2報)

최규석,Choi Kyu Suck 대한화학회 1974 대한화학회지 Vol.18 No.5

p-Phenylenediamine(PPD) 및 m-aminophenol(MAP)를 몰비를 달리하면서, -5∼0$^{\circ}$, $N_2$ 기류중에서 일정량의 포르말린(이때 포름알데히드의 량은 PPD와 MAP 전량에 대하여 2배몰에 해당하는 량으로 고정)과 반응시키면 약간의 발열과 함께 급격히 부가축합이 진행되어 난용성인 갈색 내지 등색의 중합체를 생성한다. PPD:MAP의 몰비가 1:3, 1:2, 1:1의 것들을 180∼220에서 몰비가 2:1, 3:1의 것들을 250∼270$^{\circ}$에서 각각 암색으로 색변화를 이르킬 따름이며, 이 중합체들은 모두 300$^{\circ}$까지 용융하지 않는다. 이들 중합체의 메틸렌블루에 대한 흡착력은 N2 기류중에서 중합시킨것을 묽은(7%) 수산화나트륨으로 처리하였을때 현저히 흡착력이 증가되어 PPD-MAP-F(F;포름알데히드)의 몰비가 1:3:8 일때 수지 1g당 80mg의 메틸렌블루를 흡착하며, 브롬페놀블루에대한 흡착력은 PPD-MAP-F의 몰비가 2:1:6일때가 최고이며, 수지 1g당 250mg의 브롬페놀블루를 흡착한다. TGA에 의한 내열성실험에서는 PPD-MAP-F의 몰비가 1:3:8인 경우 가장 좋은 결과를 나타냈으며, $N_2$ 기류중 매분 2$^{\circ}$로 가열하였을때 900$^{\circ}$에서 45%의 중량손실을 나타내었다. When mixture of p-phenylenediamine (PPD) and m-aminophenol (MAP) were reacted with formaldehyde (F) varying their amounts under $N_2$ stream at the temperature of -5∼0$^{\circ}$, addition condensation reaction occurred and brown colored resins(in some cases orange colored) were formed immediately. All resins thus formed were insoluble in most ordinary organic solvents and did not melt up to 300$^{\circ}$. When the resins were treated with dilute(7 %) aqueous sodium hydroxide solution, the adsorptivity of methylene blue on them showed marked improvement reaching as much as 80 mg of methylene blue on 1 g of the resin. On the other hand, in the case of bromophenol blue, its amount of adsorption appeared 250 mg per 1 g of the resin. The TGA under $N_2$ atmosphere indicated that the resin formed in molar ratio of 1 : 3 : 8 (PPD : MAP : F) showed the best heat-resistant property among others. About 40 % weight loss was observed for this resin at 900$^{\circ}$ with heating rate of 2$^{\circ}$ per minute.

芳香族디아민 및 아미노페놀-포름알데히드系 樹脂에 관한 硏究 (第1報)

최규석,이하정,진재혁,Kyu Suck Choi,Ha Jung Lee,Jae Hyuk Jin 대한화학회 1973 대한화학회지 Vol.17 No.1

m-Phenylenediamine(MPD) 및 m-aminophenol(MAP)을 각각 질소기류중, pH1, m-Phenylenediamine(MPD) 및 m-aminophenol(MAP)을 각각 窒素氣流中, pH1, $-5{\sim}0^{\circ}C$에서 포름알데히드와 반응시키면 약간의 發熱과 함께 附加縮合反應이 진행되어 不溶性인 重合體를 生成한다. 또한 같은 反應 條件下에서 恐縮合反應體도 生成하며, 生成 重合體의 耐熱性 및 Bromophenol Blue 또는 Methylene Blue의 吸着性은 恐縮合重合體의 경우가 우수하다. MPD-MAP-F계(F: 포름알데히드) 恐縮合樹脂는 TGA에서 몰比 1:2:6의 경우, $800^{\circ}C$에서 각 $40\%$의 重量 損失을 나타내는 좋은 耐熱性을 띄며, 몰比 2:1:6의 恐縮合樹脂는 1g당 Bromophenol Blue를 308mg을 吸着하는우수한 吸着性을 띈다. When m-phenylenediamine (MPD) or m-aminophenol (MAP) was treated with formaldehyde(F), under $N_2$ stream, at the temperature $-5\sim0^{\circ}C$, addition condensation occurred and insoluble resins formed immediately. Under the same reaction conditions m-phenylenediamine, m-aminophenol and formaldehyde also easily copolycondensed and insoluble MPD-MAP-F type copolymer formed. MPD-MAP-F type copolycondensed resin was superior in both heat-resistant property and adsorptivity of Bromophenol Blue or Methylene Blue than the MPD-F and MAP-F type resins. From the result of TGA, under $N_2$stream, MPD-MAP-F resin showed about $40\%$ weight loss at $800^{\circ}C$, and this type of resin 1g adsorbed 308mg of Bromophenol Blue.

폴리스티렌유도체계 킬레이트수지의 컬럼크로마토그래피법에 의한 중금속이온의 분리에 관한 연구

최규석(Kyu Suck Choi),정택상(Taik Sang Chung) 한국고분자학회 1983 폴리머 Vol.7 No.2

무기입자 충전 Polypropylene 의 기계적 및 유성학적 성질

최규석(Kyu Suck Choi),김척기(Chuck Ki Kim) 한국고분자학회 1987 폴리머 Vol.11 No.2

금속이온결합성 고분자킬레이트에 관한 연구 ( 제2보 )

최규석(Kyu Suck Choi),송성현(Sung Hyun Song) 한국고분자학회 1979 폴리머 Vol.3 No.2