Copper 촉매를 이용한 p-phenylenediamine (PPD) 합성에 관한 연구

김정석; 이상용; 이정호; 최원춘; 강나영; 박선영; 김기웅; 임종성; 박용기; 서휘민; Jungsuk Kim; Sang-yong Lee; Jungho Lee; Won Choon Choi; Na Young Kang; Sunyoung Park; Kiwoong Kim; Jong Sung Lim; Yong-Ki Park; Hwimin Seo

Korean Chemical Engineering Research, Vol.54, No.3, 425-430, June, 2016

DOI10.9713/kcer.2016.54.3.425 Export Citation

Copper 촉매를 이용한 p-phenylenediamine (PPD) 합성에 관한 연구

A Study on the Synthesis of p-phenylenediamine (PPD) Using Copper Catalyst

김정석^{1, 2}, 이상용^{1, 2}, 이정호¹, 최원춘¹, 강나영¹, 박선영¹, 김기웅¹, 임종성², 박용기¹, 서휘민^{1, 2, †}

¹한국화학연구원 탄소자원전환연구센터, 34114 대전시 유성구 가정로 141
²서강대학교 화공생명공학과, 04107 서울특별시 마포구 백범로 35

Jungsuk Kim^{1, 2}, Sang-yong Lee^{1, 2}, Jungho Lee^{1, 3}, Won Choon Choi^{1, 3}, Na Young Kang^{1, 3}, Sunyoung Park^{1, 3}, Kiwoong Kim^{1, 3}, Jong Sung Lim², Yong-Ki Park^{1, 3}, and Hwimin Seo^{1, 2, †}

¹Center for Carbon Resources Conversion, Korea Research Institute of Chemical Technology, 141, Gajeong-ro, Yuseong-gu, Daejeon, 34114, Korea
²Chemical and Biomolecular Engineering, Sogang University, 35, Baekbeom-ro, Mapo-gu, Seoul, 04107, Korea
³, Korea

E-mail:

초록

액체 암모니아와 p-diiodobenzene (PDIB)을 반응물로, Cu계 화합물을 촉매로 사용하는Aromatic amination을 이용하여 p-phenylenediamine (PPD)을 합성하였다. 촉매의 종류와 양, 환원제의 종류, 암모니아의 양, 반응 온도가 생성물의 분포에 미치는 영향을 조사하였다. Cu(I) 화합물과 Cu 분말은 촉매로서 작용한 반면 Cu(II) 화합물은 촉매로서 작용하지 않았다. 촉매의 양이 증가할수록 반응속도는 빨라지지만 부반응물인 aniline의 생성량도 증가하였다. Aniline 생성량은 또한 사용한 암모니아의 양이 증가할수록 감소하였다. 촉매 사용량을 줄이기 위해 환원제인 ascorbic acid, hydrazine, dihydroxyfumaric acid를 조촉매로 사용하면 반응속도가 크게 향상되었으나 부반응물인 aniline의 생성량 또한 증가하였다. 사용한 조촉매 중에서는 ascorbic acid와 dihydroxyfumaric acid를 사용하였을 경우가 hydrazine을 사용하였을 경우보다 반응속도가 빨랐고, dihydroxyfumaric acid를 사용하였을 경우 가장 적은 양의 aniline이 생성되었다.

p-Phenylenediamine (PPD) was synthesized by aromatic amination of p-diiodobenzene (PDIB) using liquid ammonia and Cu-catalysts. The effects of the catalyst, reductant, ammonia quantity and reaction temperature on PPD production were investigated. Cu(I) compounds and Cu powder were selected as catalyst due to a higher selectivity than Cu(II) compounds. As the catalyst quantity increased, rate of PPD production as well as side reaction of aniline decreased with increasing the quantity of ammonia. Reductants such as ascorbic acid, hydrazine and dihydroxyfumaric acid were tested to lower the catalyst loading. The use of reductants resulted in increasing the reaction rate but also increased the amount of aniline The rate of reaction using ascorbic acid or dihydroxyfumaric acid was faster than that using hydrazine. The lowest side reaction of aniline was found in dihydroxyfumaric acid of reductants investigated.

Keywords:p-phenylenediamine;p-diiodobenzene;copper(I) catalysts;amination;dehalogenation

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[3] Smiley RA, Phenylene- and Toluenediamines in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim (2002).

[4] Beletskaya IP, Chepracov AV, Organometallics, 31, 7753 (2012)

[5] Seo HM, Park YK, Song BS, Noh HD, “Method for Manufacturing Phenylenediamine Containing Recovery Process of Iodine,” Korea Patent No. 10-1482664(2015).

[6] Shimizu A, Yamataka K, “Method for Producing Iodine or Iodine Derivatives,” U.S. Patent No. 4487752(1984).

[7] Herkelmann R, Rudolph W, Seffer D, “Method of Recovering Iodine,” U.S. Patent No. 5356611(1994).

[8] Rule M, Lane DW, Larkins TH, Tustin GC, “Process for Preparing Iodinated Aromatic Compounds”, U.S. Patent No. 4746758(1988).

[9] Kim HS, Cha IH, Lim JB, “Method of Preparing Iodinated Aromatic Compounds with High Yield,” Korea Patent No. 10-1123148(2012).

[10] Aubin Y, Fischmeister C, Thomas CM, Renaud JL, Chem. Soc. Rev., 39, 4130 (2010)

[11] Xu H, Wolf C, Chem. Commun., 3035 (2009)

[12] Wang D, Qian AB, Cai A, Ding K, Adv. Synth. Catal., 351, 1722 (2009)

[13] Xu HJ, Liang YF, Cai ZY, Qi HX, Yang CY, Feng YS, J. Org. Chem., 76, 2296 (2011)

[14] Ji P, John HA, Michael IP, J. Org. Chem., 77, 7471 (2012)

[15] Mansour M, Giacovazzi R, Ouali A, Taillefer M, Jutand A, Chem. Commun., 6051 (2008)

[16] Cho HK, Lim JS, Korean Chem. Eng. Res., 53(1), 53 (2015)

[17] Tye JW, Weng Z, Giri R, Hartwig JF, Angew. Chem.-Int. Edit., 49, 2185 (2010)

[18] Fier PS, Luo JW, Hartwig JF, J. Am. Chem. Soc., 135(7), 2552 (2013)