Ammonium fluoroborate production and determination of production parameters

Abstract

In this study, the production parameters of ammonium fluoroborate (NH4BF4) synthesis with reaction between boric acid and ammonium hydrogen fluoride were investigated. For this purpose, the effects of parameters such as reactive feeding ratio, reaction temperature, stirring rate, stirrer type, second solvent effect determined separately. Surface morphologies and structural analysis of the crystals obtained after reaction were determined by XRD, FT-IR and SEM analysis respectively. The optimum production conditions were found as reactant feeding rate 1:2, reaction temperature 90 oC, stirring type hot air stirring. Limited oxygen index test results showed that ammonium fluoroborate exhibits excellent flame retardance.

Keywords

• Boron
• ammonium fluoroborate
• flame retardant
• boric acid
• ammonium hydrogen fluoride

Amonyum floroborat üretimi ve üretim parametrelerinin belirlenmesi

Abstract

Bu çalışmada, borik asit ve amonyum hidrojen florürün reaksiyonu ile amonyum floroborat (NH4BF4) üretimine ait üretim parametreleri incelenmiştir. Bu amaçla, reaktif besleme oranı, reaksiyon sıcaklığı, karıştırma hızı, karıştırıcı cinsi, ikinci çözücü etkisi parametrelerinin etkileri ayrı ayrı belirlenmiştir. Reaksiyon sonucu elde edilen kristallerin yapısal analizleri ve yüzey morfolojileri ise sırasıyla XRD, FT-IR ve SEM analizleri yapılarak aydınlatılmaya çalışılmıştır. Amonyum floroborat üretimi için en uygun reaksiyon şartları; reaktif besleme oranı, 1:2; reaksiyon sıcaklığı, 90 oC; karıştırıcı cinsi, sıcak hava şeklinde tespit edilmiştir. Limit oksijen indeksi analizleri, amonyum floroboratın mükemmel alev geciktirici olduğunu göstermiştir.

Keywords

• Bor
• amonyum floroborat
• alev geciktirici
• borik asit
• amonyum hidrojen florür

References

1. [1] Clark M. J. R., Lynto, H., Crystal structures of potassium, ammonium, rubidium, and cesium tetrafluoborates, Can. J. Chem, 47, 2579-2586, 1969.
2. [2] Smith R. A., Mcbroom R. B., 4th edition, Kirk Othmer Encyclopedia of Chemical Technology, Chap.4: Boron Compounds, John Wiley & Sons, Inc., New York, 1992.
3. [3] Dale, L. P., 2.nd edition, Handbook of Inorganic Compounds, CRC Press, New York, 2011.
4. [4] Thomas J. S., James A.G., Manufacture of Ammonium Fluoroborate, U.S. Pat. 2,799,556, July. 16, 1957,
5. [5] Booth H. S., Rhemar S., Inorganic Synthesis, Chap.2, McGraw-Hill Book Co., New York, 1946.
6. [6] Arıkan Y., İyonik sıvı katalizörlüğünde bazı organik tepkimeler ve özellikleri, Yüksek Lisans Tezi, İnönü Üniversitesi, Fen Bilimleri Enstitüsü, Malatya, 2005.
7. [7] Kehe H. J., Johnson R. T., Driscoll W. J., Bloor R. R. (to B. F. Goodrich Co.), U.S. Pat. 3,071,619, Jan. 1, 1963.
8. [8] Natsuhisa O., Takeshi W., Kazuhiko S., Diastereocontrolled synthesis of dinucleoside phosphorotioates using a novel class of activators, dialkyl(cyanomethyl) ammonium tetrafluoroborates, J. Am. Chem. Soc, 124, 4962-4963, 2002.

9. [9] Ramon A., Laureano C., Pedro G., Jose-Maria S., Ignacio V., ethylbenzene oxidation with air catalysed by bis(acetylacetonate)nickel(ıı) and tetra-n-butylammonium tetrafluoroborate, Appl Catal A-Gen, 203, 259-268, 2000.
10. [10] Keith R. B., Neil B., N-vinylpyridinium and -ammonium tetrafluoroborate slts: New electrophilic coupling partners for PD (0) – Catalyzed Suzuki Cross- Coupling Reactions, Org Lett, 9, 4, 707-710, 2007.
11. [11] Chıou-Ling C., Man-Kit,L., Mei-Hui,Y., Alkyl and dialkylammonium tetrafluoborate catalyzed cis-trans isomerization of 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, Tetrahedron, 60, 9205-9212, 2004.
12. [12] Hang W. J., Kartal S. N., Shinoda K., Imamura Y., Surface treatment for preventing decay and termite attack in wood using didecycl dimethyl ammonium tetrafluoroborate (DBF) ıncorparated with acryl-silicon type resin, Holz als Roh- und Werkstoff, 63, 204-208, 2005.
13. [13] Won-Joung H., Kartal S. N., Yuji I., Evaluation of new quaternary ammonium compound, didecyldimethylammonium tetrafluoroborate (DBF) in comparison with DDAC: Leachability and termite resistance tests, Holz als Roh – und Werstoff, 64, 111-116, 2006.
14. [14] Kartal S. N., Christian B., Andreas O. R., Yuji I., Biological effectiveness of didecyl dimethyl ammonium tetrafluoroborate (DBF) against basidiomycetes following preconditioning in soil bed tests, Wood Sci. Technol., 40, 63-71, 2006.
15. [15] Chong S., Xue-Mei L., Ying-Zhou L., Chun-Xi L., Effect of mono-, di- and tri-ethanolammonium tetrafluoroborate protonic ionic liquids on the volatility of water, ethanol, and methanol, Fluid Phase Equilibr, 303, 103–110, 2011.
16. [16] Todd W. H., Gabbai F. P., ammonium boranes for the selective complexation of cyanide or fluoride ıons in water, J.Am.Chem.Soc, 129, (39), 11978, 2007.
17. [17] Giuseppetti G., Mazzi F., Tadini C., Ferloni P. Zabinska G., Torre S., the crystal structure and disorder in tetrapropylammonium tetrafluoroborate, (n-C3H7)4NBF4, Z Kristallogr- Crystalline Materials, 212, (5), 367-371, 1997.
18. [18] Lileev A., Lyashchenko A., Dielectric properties of ammonium salt aqueous solutions, J.Mol.Liq.,150, 4–8, 2009.
19. [19] Marano R.T., Mcatee JR J. L., Differential thermal analysis of ammonium tetrafluoroborate and hexamminonickel- and tetramminozinc-tetrafluoroborate, Thermochim Acta, 4, (3-5), 421-424, 1972.
20. [20] Sara B., Manu L., Jussi Valkonen K. R., Synthesis, characterization and thermal behavior of nine new r2r2’n+a--type quaternary ammonium tetrafluoroborate or hexafluorophosphate salts prepared by metathesis from analogous halide salts, J.Mol.Struct.,875, 549–559, 2008.
21. [21] Petrov G.S., Volodkovich, L.M., Vecher, R.A., Vecher, A.A., Determination of heat capacity and enthalpies of phase transitions of ammonium, sodium and potassium tetrafluoroborates, Thermochim Acta, 87, 381-383, 1985.
22. [22] Yusuke I., Hiroshi A., Takefumi G., Yukihiro Y., Yosuke M., Hitoshi M., Structure and thermal property of N,N-diethyl-N-methyl-N-2-methoxyethyl ammonium tetrafluoroborate-H2O mixtures, Chemical Physics, 352, 224–230, 2008.
23. [23] Hiroshi A., Yukihiro Y., Yusuke I., Takefumi G., Hitoshi M., Phase behavior of room temperature ionic liquid – H2O mixtures: N, N-diethyl-N-methyl-N-2-methoxyethyl ammonium tetrafluoroborate, J.Mol.Liq.150, 16–21, 2009.
24. [24] Masami A., Yusuke I., Hıroshi A., Hıtoshi M., Yukıhıro Y., UV–Vis spectroscopic study of room temperature ıonic liquid–water mixtures: N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate, Thermochim Acta, 532, 179–182, 2012.
25. [25] Gobbels D., Meyer G., Aufbau und abbau von (NH4)[BF4] und H3N-BF3, Z. Anorg. Allg. Chem., 628, 1799-1805, 2002.
26. [26] Aydın Y. D., Biberoğlu R., Kümbetlioğlu F., Gürü M., Kobalt floroborat sentezi ve alev geciktirici olarak kullanılabilirliği, 1st International Eurasion Conference on Science, Engineering and Technology Ankara, Türkiye, 22-23 Kasım, 2018.
27. [27] Aydın Y. D., Gürü M., İpek D., Özyürek D., Obtainment of copper(ıı) fluoroborate by high-energy impacted ball-milling, Acta Phys.Pol.A, 135, (888-891), 2019.
28. [28] Aydın Y. D., Gürü M., Ipek D., Özyürek D., Synthesis and characterization of zinc fluoroborate from zinc fluoride and boron by mechanochemical reaction, Arab J Sci Eng, 42, 4409-4416, 2017.
29. [29] Aydın Y. D., Patlar K., Gürü M., Akkurt F., Synthesis of antimony fluoroborate and usability as flame retardant, 8th ınternational advanced technologies symposium (IATS'17) Elazığ, Türkiye, 19-22 Ekim, 2017.
30. [30] Aydın Y. D., Kurt H., Kandemir E. B., Gürü M., Synthesis of lead fluoroborate and usability as flame retardant, 8th ınternational advanced technologies symposium (IATS'17) Elazığ, Türkiye, 19-22 Ekim, 2017.
31. [31] Güngör G., Aydın Y. D., Gürü M., Kalsiyum oksitten kalsiyum floroborat sentezi ve alev geciktirici olarak kullanılabilirliği, Uluslararası Bor Sempozyumu (BORON2019) Nevşehir, Türkiye, 17-19 Nisan, 2019.
32. [32] Gürü M., Aydın Y. D., Topuz E., Akkurt F., Kuru F., potasyum karbonat ve floroborik asitten potasyum floroborat sentezi ve alev geciktirici olarak kullanılabilirliği, 13. Ulusal Kimya Mühendisliği Kongresi Van, Türkiye, 3-6 Eylül, 2018.
33. [33] Gürü M., Aydın D. Y., Sedir P., Akkurt F., Yaş yöntemle titanyum floroborat sentezi ve alev geciktirici olarak kullanılabilirliği, İleri Teknolojiler V. Çalıştayı Piri Reis Üniversitesi, İstanbul, Türkiye, 23 Ekim, 2017.
34. [34] Çelik M. S., Sodyum ve potasyum tetrafloroborat bileşiklerinin üretiminde kristalizasyon şartlarının belirlenmesi, Doktora Tezi, İnönü Üniversitesi, Fen Bilimleri Enstitüsü, Malatya, 2019.
35. [35] Bingol D., Aydogan S., Bozbas S., Wet mechanochemical processing of celestine using (NH4)2CO3, SAUJS, 20, 27-284, 2017.
36. [36] Govardhana Rao S., Mohan M. T., Krishna T. V., Rao B. S., Volumetric properties of 1-butyl-3-methylimidazolium tetrafluoroborate and 2-pyrrolidone from T=(298.15 to 323.15)K at atmospheric pressure, J. Chem. Thermodyn., 94, 127-137, 2016.
37. [37] S. Petit, D. Righi, J. Madejová, ifrared spectroscopy of NH4+-bearing and saturated clay minerals: A review of the study of layer charge, Appl Clay Sci., 34, 1, 22-30, 2006.