Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Development of New Fluorescent Whitening Agent with 4,4'-Di((E)-styryl)-1,1'-biphenyl Skeleton Attached with Aromatic Ester from Recyclable Source MFB

재사용이 가능한 MFB로부터 Aromatic Ester가 도입된 4,4'-Di((E)-styryl)-1,1'-biphenyl의 골격을 갖는 새로운 Fluorescent Whitening Agent의 개발 연구

  • Alkhalaf, Norah. S. (Department of Applied Chemistry, Kookmin University) ;
  • Kim, Seok Chan (Department of Applied Chemistry, Kookmin University)
  • Received : 2018.01.22
  • Accepted : 2018.02.25
  • Published : 2018.06.10
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Abstract

Methyl 4-formylbenzoate (MFB), a by-product of the DMT production process, which has been disposed, was used as a starting material for the synthesis of six new fluorescent whitening agent's candidates with 4,4'-di((E)-styryl)-1,1'-biphenyl skeleton attached with an aromatic ester, the same as that of the commercial product family. All candidates were synthesized by the reaction of MFB, and its derivatives with tetraethyl biphenyl-4,4'-diylbis(methylene)diphosphonate using Wittig-Horner reaction. UV spectra for all candidates were recorded and the data were used for calculating the molar absorptivity in order to confirm the usability as a fluorescent whitening agent. All of them showed overall molar extinction coefficients (log ${\varepsilon}$ 4.59~5.00) similar to those of conventional commercial products (log ${\varepsilon}$ 4.85). In particular, compounds 16 and 17 having a dimethoxyphenyl group exhibited a molar extinction coefficient superior to those of conventional commercial products, and thus a field testing for commercialization will be conducted.

DMT 생산과정의 부산물로서 폐기 처리되어 왔던 methyl 4-formylbenzoate (MFB)를 출발 물질로 하여 고급 형광 증백제 family와 동일한 4,4'-di((E)-styryl)-1,1'-biphenyl 기본 골격을 갖고 aromatic ester가 도입된 새로운 형광 증백제(fluorescent whitening agent) 후보 물질 6종을 합성하였다. 후보 물질 6종은 MFB 및 그의 유도체와 tetraethyl biphenyl-4,4'-diylbis(methylene)diphosphonate와 Wittig-Horner 반응을 이용하여 합성하였다. 합성된 6종에 대하여 형광증백제로의 가능성을 확인하기 위하여 UV 스펙트럼을 기록하여 흡광 계수를 얻었으며, 6종 모두 전반적으로 기존 상용 제품(log ${\varepsilon}$ 4.85)과 유사한 몰 흡광 계수(log ${\varepsilon}$ 4.59~5.00)를 보여주고 있다. 특별히 화합물 디메톡시 페닐그룹을 갖는 16, 17은 기존 상용 제품보다 우수한 몰흡광 계수를 나타내고 있어 상용화를 위한 현장 테스트를 진행할 예정이다.

Keywords

References

  1. A. R. Mitchell, P. F. Pagoria, and R. D. Schmidt, A new synthesis of TATB using inexpensive starting materials and mild reaction conditions, 27th International Annual Conference ICT on Energetic Materials, June 25-28, Karlsruhe, Germany (1996).
  2. A. R. Mitchell, P. F. Pagoria, and R. D. Schmidt, New synthesis of TATB process development studies, 29th International Annual Conference ICT on Energetic Materials. June 30-July 3, Karlsruhe, Germany (1998).
  3. K. D. Kim, Y. Yu, H. J. Jeong, M. J. Ham, K. L. Kim, A. N. Kim, O. Davgajantsan, G. S. Park, and S. C. Kim, Development on recovery of MFB from industrial waste without second pollution, Bull. Korean Chem. Soc., 33, 4275-4276 (2012). https://doi.org/10.5012/bkcs.2012.33.12.4275
  4. S. H. Kim, Y. Ryu, J. C. Kim, and S. C. Kim, Recovery of MFB generated from dimethyl terephthalate production process, Appl. Chem. Eng., 26, 621-623 (2015). https://doi.org/10.14478/ace.2015.1045
  5. K. D. Kim, Y. Ryu, and S. C. Kim, Facile one-pot synthesis of PABA from MFB, Appl. Chem. Eng., 25, 337-339 (2014). https://doi.org/10.14478/ace.2014.1020
  6. Y. Ryu, J. C. Kim, M. J. Ham, and S. C. Kim, Process development of 4,4'-bis(2-benzoxazolyl)stilbene from recyclable source MFB, Appl. Chem. Eng., 27, 195-198 (2016). https://doi.org/10.14478/ace.2016.1012
  7. J. C. Kim, Y. Ryu, and S. C. Kim, Practical process development of AMCA from recyclable source MFB, Appl. Chem. Eng., 27, 508-511 (2016). https://doi.org/10.14478/ace.2016.1073
  8. H. J. Chung, Y. S. Yang, and S. C. Kim, Development of new fluorescent whitening agent with 4,4'-di((E)-styryl)-1,1'-biphenyl skeleton from recyclable source MFB, Appl. Chem. Eng., 28, 294-298 (2017).
  9. K. Weber and C. Luethi, Styryl compounds, process for their manufacture and their use, US Patent 3,825,534 (1974).
  10. A. E. Siegrist, P. Liechti, H. R. Meyer, and K. Weber, Aromatic compounds containing ethylene double bonds, processes for their manufacture and use, US Patent 3,991,049 (1976).
  11. L. Guglielmetti, H. R. Meyer, D. Reinehr, and K. Weber, Mixtures of fluorescent whitening agents, US Patent 4,867,906 (1989).
  12. R. J. Sundberg, P. A. Buckowork, and F. O. Holcombe, Preparation of esters of 4-alkyl-2,4-pentadienoic acids by the phosphonate modification of the Wittig reaction, J. Org. Chem., 32, 2938-2941 (1967).
  13. H. Pommer, H. P. Siebel, R. Schwen, and W. Stilz, Macromolecular substances optically brightened with 1,4-bis-styryl-benzenes, US Patent 3,177,153 (1965).
  14. W. Stilz, and H. Pommer, Production of compounds of the 1,4-divinylbenzene series, US Patent 3,177,208 (1965).