Chlorobenzyl alcohol을 이용한 total isocyanate의 가스크로마토그래프 분석법 개발 = (The)development of gas chromatographic method of total isocyanate using chlorobenzyl alcohol

국문 초록 (Abstract)

Isocyanate류는 OECD의 high production volume(HPV) chemical list에 등록되어있다. Isocyanate에 노출시 피부, 눈 및 호흡기계의 염증, 천식, 기관지염, 그리고 폐부종 등을 발생시킨다.TDI의 발암성에 대해서 IARC는 Griop 2B로, 그리고 NTP는 Group B로 지정되어있다. 1984년 12월 3일 인도 보팔에서 발생한 isocyanate 누출 사고로 인해서 3,500여명이 사망하고 100,000명 이상이 후유증을 보이고 있다.TDI, MDI 및 HDI에 대한 ACGIH의 TWA는 0.005ppm(0.04 ㎎㎥)이고, STEL는 0.02 ppm (0.14 ㎎㎥)이다. NIOSH와 OSHA의 TDI, MDI 및 HDI에 대한 HPLC 분석법은 임핀저나 glass fiber filter로 포집하는데 이 방법은 다른 물질의 간섭과 재현성이 좋지 않다. 최근 NIOSH에서 9-anthracenylmethyl 1-piperazinecarboxylate를 이용하여 유도체화한 후 sodium thiomethoxide와 반응시켜서 생성된 9-anthracenylmethyl methyl sulfide를 HPLCUVD․FD로 분석하는 Total isocyanate 분석방법에 대하여 연구하고 있지만, 복잡한 분석과정, 이물질에 의한 간섭, 수율 등의 문제를 갖고 있다.따라서 본 연구는 2-CBA를 이용하여 2,4-TDI, 2,6-TDI, 4,4''-MDI 및 1,6-HDI를 유도체화 및 가수분해하여 GCFID, GCECD 및 GCMSD 분석법을 설정하고자 한다.2,4-TDI, 2,6-TDI, 4,4''-MDI 및 1,6-HDI와 2-CBA를 반응시켜서 4TC-urethane, 6TC-urethane, MC-urethane 및 HC-urethane이 합성되었으며 합성수율은 각각 71.7%, 79.6%, 92.54% 및 96.94%이었다.합성된 4TC-urethane, 6TC-urethane, MC-urethane 및 HC-urethane은 TLC, GCFID, GCPD-ECD 및 GCMSD로 정성 및 정량적으로 확인하였다.2-CBA로 코팅된 glass fiber filter를 87℃, 20mmHg로 1hr 이상 건조처리 하였을 때 모두 증발하였지만 4TC-urethane, 6TC-urethane, MC-urethane 및 HC-urethane 코팅된 glass fiber filter를 같은 조건에서 처리하였을 경우 3hr까지 증발하지 않았다.4TC-urethane의 추출법을 이용한 가수분해 수율은 1, 3, 5N HCl 및 1, 3, 5N H2SO4에서 약 100% 이었다.또한, 4TC-urethane, 6TC-urethane, MC-urethane, HC-urethane 및 urethane들의 혼합 urethane은 0.1N HCl 용액과 Ethyl cellosolve를 사용하여 가수분해 한 후 직접 주입한 방법에 의한 가수분해 수율은 약 100% 가량이었다.4TC-urethane, 6TC-urethane, MC-urethane 및 HC-urethane을 가수분해하여 생성된 가수분해물인 2-CBA는 GCFID, GCPD-ECD 및 GCMSD에 의해 정성 및 정량적으로 분석되었으며, LOD는 각각 9.69ppm, 11.03ppm 및 0.38ppm이었다.2-CBA의 GCFID, GCPD-ECD 및 GCMSD에서의 최저 분석농도는 각각 2.5ppm, 10ppm 및 0.01ppm이다. 1.5ℓmin의 유량으로 6시간 포집하고 최저 분석농도를 기준으로 하였을 때 대기 중의 최저 2,4-TDI의 분석 가능농도는 각각 5.67㎍㎥, 22.69㎍㎥ 및 0.02269㎍㎥으로써 ACGIH의 TDI에 대한 TWA인 0.04㎎㎥을 포함한 Isocyanate류의 TWA보다 낮으므로 total isocyanate의 새로운 GC　분석법으로써 가능성이 있다. 그리고, 만약 좀더 감도가 좋은 알콜류를 사용한다면 GCPD-ECD에서 더 낮은 농도까지 분석 가능할 것이다.따라서 2,4-TDI, 2,6-TDI, 4,4''-MDI 및 1,6-HDI를 동시 분석하는 Total Isocyanate 분석이 GCFID, GCPD-ECD 및 GCMSD로 가능하다.

다국어 초록 (Multilingual Abstract)

Isocyanates are registered in OECD''s high production volume(HPV) chemical list. Exposure to isocyanate causes inflammation in the skin, eyes and respiratory system as well as asthma, bronchitis and pulmonary edema.In terms of TDI''s carcinogenesis, the IARC categorizes it as Group 2B and the NTP as Group B. The isocyanate leakage accident that occurred in Bhopal, India on December 3, 1984 left 3,500 dead and more than 100,000 with aftereffects.The ACGIH''s TWA for TDI, MDI and HDI are 0.005ppm(0.04 ㎎㎥) and the STEL is 0.02 ppm (0.14 ㎎㎥).The HPLC analytical method for TDI, MDI and HDI used by the NIOSH and the OSHA involves a collection mechanism with an impinger or a glass fiber filter, but the method is less than desirable in terms of interference with other substances and repeatability.Recent studies conducted by the NIOSH deal with the total isocyanate analytical method, which involves derivation using 9-anthracenylmethyl 1-piperazinecarboxylate and analyzing the 9-anthracenylmethyl methyl sulfide generated from the sodium thiomethoxide reaction with HPLCUVD․FD. However, it also carries problems of complicated analytical procedures, interference with foreign substances and the yield.Accordingly, this study proposes the GCFID, GCPD-ECD and GCMSD analytical method which involves derivation and hydrolysis of 2,4-TDI, 2,6-TDI, 4,4''-MDI and 1,6-HDI using 2-CBA.2,4-TDI, 2,6-TDI, 4,4''-MDI and 1,6-HDI reacted to 2-CBA to synthesize urethanes, and the yield was 71.7% and 79.6%, 92.54% and 96.94% respectively.Synthesized 4TC-urethane, 6TC-urethane, MC-urethane and HC-urethane confirmed by the TLC, GCFID, GCPD-ECD and GCMSD quantitatively and qualitatively.Whereas dry processing a glass fiber filter coated with 2-CBA at 87℃ and 20mmHg for 1 hour resulted in complete elimination, performing similar processing for a glass fiber filter coated with 4TC-urethane, 6TC-urethane, MC-urethane and HC-urethane did not yield a change in content for 3 hours.The hydrolysis rate of 4TC-urethane according to the hydrolysis conditions(1, 3, 5N HCl and H2SO4) was about 100%. by extraction method.Moreover, 4TC-urethane, 6TC-urethane, MC-urethane, HC-urethane, and the composite urethane consisting of these urethanes also displayed a hydrolysis rate of about 100% using 0.1N HCl and ethyl cellosolve by direct injection method.The hydrolysate 2-CBA from 4TC-urethane, 6TC-urethane, MC-urethane and HC-urethane was quantitatively and qualitatively analyzed in the GCFID, GCPD-ECD and GCMSD, the LODs were 9.69ppm, 11.03ppm and 0.38ppm, respectively.2-CBA''s lowest concentration analyzed by GCFID, GCPD-ECD and GCMSD were 2.5ppm, 10ppm and 0.01ppm, respectively.When 2-CBA''s lowest concentration analyzed by GCFID, GCPD-ECD and GCMSD were applied (1.5ℓmin, collected for 6 hours) the lowest analyzable TDI concentration in the atmosphere were 5.67㎍㎥, 22.69㎍㎥ and 0.02269㎍㎥ (ACGIH TWA : 0.04 ㎎㎥). Because the lowest analyzable TDI concentration in the atmosphere are lower than ACGIH''s TWA of isocyanate including TDI, this method is feasible as new GC method of total isocyanate.The more sensitive alcohols, the more low concentration can be analyzed by GCPD-ECD.Therefore, simultaneous analyses of 2,4-TDI, 2,6-TDI, 4,4''-MDI and 1,6-HDI, along with a total isocyanate analysis, are feasible with GCFID, GCPD-ECD and GCMSD