感光性 樹脂에 關한 硏究 (第11報). Naphthoquinone-1,2-diazide-5-sulfonyl Esters의 光分解反應

심정섭,강두환,Shim Jyong Sup,Kang Doo Whan 대한화학회 1975 대한화학회지 Vol.19 No.4

Polyglyceryl phthalate, bisphenol A-epichlorohydrin 縮重合物 및 polyvinyl alcohol의 naphthoquinone-1,2-diazide-5-sulfonyl esters(PGND, BEND 및 PVAND)에 대해 未增感 및 增感한 경우의 IR 스펙트럼을 측정하여 그들의 光分解機構를 硏究하였다. o-quinonediazide에 기인하는 C=N= 및 C=0의 흡수가 露光에 의해 減少내지는 消失하고있었고 또한 indene carboxylic acid의 C=0 흡수강도가 증가되고 있는 것으로 보아 o-quinonediazide group 이 光에 依하여 分解하여 알카리 수용액에 가용성인 indene carboxylic acid로 분해되는 것으로 추정된다. 한편, 露光時間에 대한 增感 및 未增感試料의 吸收强度의 變化를 측정하므로서 增感劑의 增感效果도 아울러 검토하였다. The degradation mechanisms of naphthoquinone-1,2-diazide-5-sulfonyl esters(PGND, BEND and PVAND) of polyglyceryl phthalate (PG), bisphenol A-epichlorohydrin (BE) and polyvinyl alcohol (PVA) were studied by infrared absorption spectra. Absorption band due to C=N=and C=O of o-quinonediazide group decreased or disappeared after sufficient exposing to light. And also, absorption band C=O of indene carboxylic acid was increased. From the results, it may be concluded that the above photosensi tive polymers were dissociated to indene carboxylic acid soluble in aqueous alkali solution. Further, the effect of sensitizers were examined by the variation of intensity in infrared absorption spectra of sensitized and unsensitized samples.

感光性 樹脂에 關한 硏究 (第10報). Naphthoquinone-1,2-diazide-5-sulfonyl Esters의 感光性과 分光感度

심정섭,강두환,Shim Jyong Sup,Kang Doo Whan 대한화학회 1975 대한화학회지 Vol.19 No.4

合成한 pllyglyceryl phthalate, bisphenol A-epichlorohydrin 축중합물과 polyvinyl alcohol의 naphthoquinone-1,2-diazide-5-sulfonyl esters(PGND, BEND 및 PVAND)의 感光特性을 지배하는 諸因子를 이들에 대한 光照射前後의 溶解度 차이에 의하여 檢討하였다. 유리 또는 石英支持薄板上에 塗布한 各試料를 各種條件下에서 露光하고 알카리 水溶液에 침지시킨 다음 塗布된 필림의 殘膜收率(W/W0)을 計算하였다. 필름의 感光度와 직접적인 관계가 있는 殘膜收率은 母體樹脂의 重合度, 增感劑의 種類 및 添加濃度에 따라 영향이 있었다. 母體樹脂의 重合度가 크면 클수록 感光性이 더 우수하였으며, 增感劑의 添加濃度는 5%일때가 가장 좋은 效果를 나타내었다. PGND, BEND 및 PVAND에 대해 본실험에서 사용한 各種 增感制 중에서 가장 效果的인 것은 benzanthrone, 5-nitroacenaphthene, picramide이였다. 이들 樹脂와 增感劑를 添加한 경우의 固相에 있어서의 紫外線吸收스펙트럼과 感色性 寫眞을 각각 비교 검토하여 그 增感과 分光感度的 特性을 糾明하였다. PGND, BEND 및 PVAND는 使用한 增感制에 의하여 光學增感하였으며 增感效果가 현저한 것일수록 그 感光波長城이 長波長쪽으로 伸張하였다. 未增感, 增感試料에 있어서 分光吸收 極大 波長城과 分光感光極大波長城이 거의 一致하고 있는 점으로 보아 試料 樹脂들에 의해서 吸收된 波長城의 光은 그 分野에 有效하게 使用되고 있음을 확인하였다 Photosensitive properties of naphthoquinone-1,2-diazide-5-sulfonyl esters (PGND, BEND and PVAND) of polyglyceryl phthalate(PG), bisphenol A-epichlorohydrin condensate(BE) and polyvinyl alcohol(PVA) were investigated by the change of solubility before and after exposing to light. Various samples coated on glass or quartz plates were exposed to light under various conditions and steeped in aqueous alkali solution, and then the yield of residual film(W/W0) was determined. The yield of residual film, which was closely related to the sensitivity of the film, was affected by the degree of polymerization of the backbone resin, sensitizers and their concentration. In polymer homologs, the sensitivity was dependent on the degree of polymerization(the higher, the better). And also, it was most effective when 5 % of sensitizers to esters was used. The minimum exposed time was 0.6 min. for PGND-1, 1.0 min. for BEND-1, and 3.0 min. for PVAND-1. Most effective sensitizers for PGND, BEND and PVAND among those used here were benzanthrone, 5-nitroacenaphthene and picramide, respectively. The spectral sensitivities of PGND, BEND and PVAND were examined by comparing their spectrograms with UV-spectra in a solid state. Also, the sensitization and spectral sensitivity of the above polymers were studied. All the polymers containing the sensitizers showed optical sensitization. From the fact that in either case of sensitized or unsensitized sample, the ranges of absorption-maximum wave length were almost consistent with sensitivity maximum wave length, it was proved that the light absorbed by a sample served efficiently for photochemical reactions. Benzanthrone was found to be an excellent sensitizer for PGND.

Epoxy 樹脂에 關한 硏究 (第 1 報) Naphthylamines 及 Aromatic amines 과 Epichlorohydrin과의 重合物에 關하여

심정섭,홍성일,Shim, Jyong-Sup,Hong, Sung-Il 대한화학회 1961 대한화학회지 Vol.5 No.1

Nowadays, it is a well-known fact that the epoxy resins play an important role in the industrial field of plastics because of their excellent properties. Although studies on the polymers of epichlorohydrin with phenols, up-to-date, were various, there were only a few wokrs on the polymers of epichlorohydrin with amines. Therefore the experiments are carried out about the polymerization of epichlorohydrin with ${\alpha}-, {\beta}$-naphtylamine, o-, m-, p-toluidine, and o-, m-, p-nitroaniline. Examining the polymerization processes and the differences in the properties of the polymers, we obtained the following conclusions. 1) ${\alpha}$-naphthylamine, ${\beta}$-naphthylamine, o-toluidine, m-toluidine and p-toluidine react with epichlorohydrin to form polymers but o-, m-, and p-nitroaniline do not make polymers with epichlorohydrin. 2) As polymerization times after adding sodium hydroxide and refluxing again 3hrs. are suitable for ${\alpha}$-naphthylamine-epichlorohydrin, 3.5hrs. for${\beta}$-naphthylamine-epichlorohydrin, and 4hrs, for m-toluidine-epichlorohydrin. 3) Method for determining molecular weight of these polymers by the titration of end group is applicable to the polymers having D.P. less than about 200 for ${\alpha}$-, ${\beta}$-naphthylamine-epichlorohydrin and those having D.P. less than 18 for m-toluidine-epichlorohydrin. 4) Gererally, these polymers get special colors so that these need proper pigmentation to use as molding compounds.

Telomerization 에 關한 硏究 (I) Vinyl Acetate 와 Chlorinated Hydrocarbons 과의 Telomerization 에 關하여

심정섭,홍석주,Shim, Jyong-Sup,Hong, Suck-Joo 대한화학회 1962 대한화학회지 Vol.6 No.1

The telomerization of vinyl acetate with carbon tetrachloride, chloroform and monochlorobenzene were investigated with respect to the synthesis of those telomers, properties and molecular weights of the formed telomers, and reaction mechanisms. Vinyl acetate reacted with carbon tetrachloride and chloroform to form telomers at 70-90$^{\circ}C$ and 60-70$^{\circ}C$, respectively and it formed polymer with monochlorobenzene. As a chain transfer agent, carbon tetrachloride was more effective than chloroform. In the telomerization of vinyl acetate and carbon tetrachloride: 1) The average molecular weight of the telomer decreased as the mole ratio of carbon tetrachloride to vinyl acetate increased. The optimum conditions for the highest yield of the telomer were as follows: Mole ratio of carbon tetrachloride to vinyl acetate : 2.5 Reaction time : 20 hours. 2) As the reaction proceeded, the refractive index and average molecular weight of the telomer increased rapidly in the first 10 hours but the increase was slow through the next 10 hours, so that, the average recurring number(n) of taxogen in the final product reached an almost definite value, i.e., 3. The telomer formed in the telomerization of vinyl acetate with carbon tetrachloride and chloroform turned to brown color in the air due to decomposition or polymerization. The suggested telomerization mechanism was supported by the hexachloroethane detected in the course of reaction.

感光性樹脂에 關한 硏究-Isophthalic acid-Cinnamic acid-Glycerine 系 縮重合物의 分子量에 關하여

심정섭,이부섭,Shim, Jyong-Sup,Lee, Boo-Sop 대한화학회 1962 대한화학회지 Vol.6 No.1

The polycondensates of isophthalic acid-cinnamic acid-glycerine system were synthesized. The molecular weights of these products were determined by two methods, viscosity method and osmotic pressure methods. In the synthesis of resin, the reaction temperature was kept at 232$^{\circ}C$ and the mole ratio of the reactants was chosen as follows: Glycerine ;1.0 Isophthalic acid ;1.0 Cinnamic acid ;2.8 Excessive cinnamic acid prevented gelation of reaction mixtures. As the solution became very dilute, reduced osmotic pressure P/C (at the concentration of solution below 0.24g/100 ml of acetone) and reduced viscosity ${\eta}_{sp}/C$ (at the concentration of solution below 0.32 g/100 ml of acetone) increased rapidly. The correspondence between molecular weights determined by the two methods made Huggin's equation applicable to the prepared polymer. The values of K and a are $2.77{\times}10^{-5}$ and 1.063, respectively.

Graft 重合에 關한 硏究-紫外線 照射에 依한 Polyvinyl alcohol 과 Styrene 의 Graft 重合에 關하여

심정섭,전경철,Shim, Jyong-Sup,Jun, Kyong-Chul 대한화학회 1962 대한화학회지 Vol.6 No.1

The graft polymerization of styrene to polyvinyl alcohol using a photosensitizer(benzophenone) and ultraviolet light was studied. Styrene was grafted onto polyvinyl alcohol up to when polyvinyl alcohol was pre-immersed in water and irradiated by ultraviolet light for 24 hours styrene solution of benzophenone(0.01 molarity). The highest percentage of graft obtained in the grafting which was proceeded in the presence of water added immediately before irradiation was 29%. The grafting was proportional to irradiation time within a certain limit of time, i.e., 24 hours, and presumably was initiated at the surface. After a certain degree of grafting a definite maximum was reached. Graft polymer prepared in this experiment showed high resistance to various solvents.

Acrolein과 Vinyl Compounds의 共重合에 關한 硏究

심정섭,전영승,Jyong Sup Shim,Young-Sung Jun 대한화학회 1969 대한화학회지 Vol.13 No.4

In order to determine the monomer reactivity ratio in copolymerization of acrolein, the copolymerization of acrolein with styrene, methyl methacrylate and vinyl acetate respectively was studied. The Q and e value of acrolein in each copolymerization were also calculated from those of monomer reactivity ratios, but the calculated values were slightly different from each other. The Q and e of acrolein for the system of acrolein-styrene copolymerization were Q = O.64 and e = O.62 respectively. Relations among the Q and e value, the composition and structure of copolymers and the mean sequence length in copolymerization were also discussed for acrolein copolymers.

Graftpolymerization of Methacrylamide onto Silk

심정섭,김영덕,Jyong Sup Shim,Young Duk Kim Korean Chemical Society 1969 대한화학회지 Vol.13 No.4

Ceric salt 를 觸媒로 使用하여 여러 가지 反應條件 下에서 絹布上에 Methancrylamide를 grafting 시키고, Schweitzer 試藥에 依한 溶解性 및 赤外線吸收 스펙트럼을 比較檢討하여 그라프드重合物의 生成을 確認하였다. 그라프트率은 溫度, 反應時間 및 Monomer濃度가 增加함에 따라 增加하였으며 그라프트率은 極大化하는 最適의 pH 値가 있음을 알았다. 그라프트率에 관한 理論式을 誘導하고 그 結果를 檢討하였다.

소결공정에 의한 Poly ( hydroxypropyl methacrylate ) Membrane 제조와 그의 투과특성에 관한 연구

심정섭,이동권,홍재민 ( Jyong Sup Shim,Dong Kweon Lee,Jae Min Hong ) 한국공업화학회 1990 공업화학 Vol.1 No.2

Poly(hydroxypropyl methacrylate) membranes and matrix devices having tertiary amine moiety were prepared by sintering method, and their permeation charateristics were investigated. The water content of this membrane was increased with decresing the pH of the medium. The permeability of this membrane was increased with decreasing the sintering pressure. Using sintered matrix device `burst effect` was found at the early stage, and initial insulin release of glucose oxidase immobilized matrix device could be controlled by glucose concentration of the solution.

열가소성 고분자를 이용한 사관능성 에폭시 수지의 강인성 향상에 관한 연구

심정섭,정호순,장정식 ( Jyong Sup Shim,Ho Soon Jung,Jyong Sik Jang ) 한국공업화학회 1990 공업화학 Vol.1 No.2

In order to improve the mechanical properties and fracture toughness of HPT 1071/DDS system, poly(aryl etherimide) (PEI) was incorporated in the resin system. In HPT 1071/DDS system, mechanical properties of cured epoxy resins were not strongly dependent on the concentration of DDS curing agent strongly. In the case of HPT 1071/DDS/PEI system, the fracture toughness and flexural properties of epoxy resins increased with increasing the concentration of PEI. SEM micrographs of cured epoxy resin indicated that the phase separation occured at the low concentration of PEI in this system. In addition, investigation of the relationship between mechanical properties and the morphology of modifed epoxy resin was undertaken in HPT 1071/DDS/PEI system.