Global Reaktiflik Parametreleri ve Bazı Spektral Sonuçlarla Polipropilenin Zincir Uzunluğuna Bağlı Kimyasal Reaktifliği

Year 2018, , 19 - 27, 31.05.2018

Tuğçe Akın Fatih Ucun , Ahmet Tokatlı

https://doi.org/10.29233/sdufeffd.412209

Abstract

Özet: Bu
çalışmada polipropilenin zincir
uzunluğuna (n) bağlı olarak kimyasal reaktifliği
ya da kararlılığı, global reaktiflik parametreleri ve bazı spektral sonuçlar
yardımıyla araştırıldı. Bu maksatla, molekülün optimizasyonları (n=1-12) B3LYP/6–311++G(d,p)
seviyesinde yapıldıktan sonra global reaktiflik parametreleri yani; E_HOMO,
E_LUMO, E_LUMO - E_HOMO enerji farkı, iyonlaşma
enerjisi, elektron ilgisi, kimyasal potansiyel, elektronegatiflik, sertlik, yumuşaklık,
elektrofilisiti ve nükleofilisiti indeks değerleri ve spektral sonuçlar yani;
IR, ¹H NMR ve ¹³C NMR spektrumları hesaplanarak
yorumlandı. Molekülün reaktifliğinin zincir uzunluğuna bağlı olarak artığı
fakat n=10’dan sonra hemen hemen sabit kaldığı görüldü. Bulunmuş bu zincir uzunluğunun
bu molekülün kimyasal özelliklerinin teorik olarak araştırmada yeterli olduğu
kanaatine varıldı.

Abstract: In the
present study, the chemical reactivity or stability of polypropylene depending
on the number of chain (n) were investigated via global reactivity parameters
and some spectral results. In this context, after the geometry optimizations of
the molecule (n=1-12) were carried out at B3LYP/6–311++G(d,p) level, the global
reactivity parameters such as; E_HOMO, E_LUMO, energy gap
between E_LUMO and E_HOMO, ionization enerjisi, electron
affinity, chemical potential, electronegativity, hardness, softness,
electrophilicity index and nucleophilicity index, and the spectral results such
as; IR, ¹H NMR and ¹³C NMR have been calculated and
commented. It was seen that its reactivity increases with increasing chain
number but, become nearly constant after n=10. We have concluded this found
chain number is enough to investigate its chemical properties as theoretical.

Keywords

Polipropilen, Zincir uzunluğu, Global parametreler, Spektrum, DFT

References

• [1] A. Heeger, “Nobel Lecture: Semiconducting and metallic polymers: The fourth generation of polymeric materials”, Reviews of Modern Physics, vol. 73 (3), pp. 681-700, 2001.
• [2] T.A. Skotheim, Handbook of Conducting Polymers, Marcel Dekker, New York, 1986.
• [3] T.A. Skotheim, R.L. Elsenbaumer, and J.R. Reynolds, Handbook of Conducting Polymers, 2nd ed. Marcel Dekker, New York, 1997.
• [4] T.A. Skotheim and J.R. Reynolds, Handbook of Conducting Polymers, 3nd ed. FL: CRC Press, Boca Raton, 2007.
• [5] Polypropylene Plastic Materials & Fibers by Porex. Available: www.porex.com.
• [6] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuj, M. Caricato, X. Li, H.P. Hratchian, A.F. Iamaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery jr, J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Lyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Gaussian Inc., Wallingford CT, 2009.
• [7] A. Frish, A.B. Nielsen, and A.J. Holder, Gauss view user manual, Gaussian Inc., Pittsburg, 2001.
• [8] H. Chermette, “Chemical reactivity indexes in density functional theory,” J. Comput. Chem., vol. 20, pp. 129-154, 1999.
• [9] R.G. Parr and P.K. Chattaraj, “Principle of maximum hardness,” J. Am. Chem. Soc., vol. 113, pp. 1854-1855, 1991.
• [10] T. Koopmans, “Ordering of wave functions and eigen-energies to the individual electrons of an atom,” Physica, vol. 1, pp. 104-113, 1933.
• [11] N. Islam and D.C. Ghosh, “A new algorithm for the evaluation of the global hardness of polyatomic molecules,” Int. J. Quant. Chem., vol. 109, pp. 917-931, 2011.
• [12] W. Yang and R.G. Parr, “Hardness, softness and the Fukui function in the electronic theory of metals and catalysis,” Proc. Natl. Acad. Sci., vol. 82, pp. 6723-6726, 1985.
• [13] R.G. Parr, L. Sventpaly, S. Liu, “Electrophilicity index,” J. Am. Chem. Soc., vol. 121(9), pp. 1922-1924, 1999.
• [14] P.K. Chattaraj, U. Sarkar, and D.R. Roy, “Electrophilicity Index,” Chem. Rev., vol. 106(6), pp. 2065-2091, 2006.
• [15] B. Wang, H.-R. Zhang, C. Huang, L. Xiong, J. Luo, and Chen X.-de, “Study on non-isothermal crystallization behavior of isotactic polypropylene/bacterial cellulose composites,” RSC Adv., vol. 7, pp. 42113-42122, 2017.
• [16] C. Firme, A.V. Grafor, and M.L. Dias, “Ethylene and propylene polymerization with bis(indenyl)zirconium/Mao catalytic systems modified by sterically demanding alcohols,” J. Poly. Scien. Part A: Poly. Chem., vol. 43(18), pp. 4248-4259, 2005.
• [17] B. Vincenzo and R. Cipullo, “Microstructure of polypropylene,” Prog. Polym. Sci., vol. 26, pp. 443-533, 2001.
• [18] A.A. Asiri, C.C. Ersanli, O. Sahin, M.N. Arshad, and S.A. Hameed, “Molecular structure, spectroscopic and quantum chemical studies of 1׳,3׳,3׳-trimethylspiro[benzo[f]chromene-3,2׳-indoline,” J. Mol. Struct. vol. 1111, pp. 108-117, 2016.
• [19] T. Hahn, W. Suen, S. Kang, S.L. Hsu, H.D. Stidham, and A.R. Siedle, “An analysis of the Raman spectrum of syndiotactic polypropylene. 1. Conformational defects,” Polymer, vol. 42, pp. 5813-5822, 2001.
• [20] F.P.T.J. van der Burgt, Crystallization of isotactic polypropylene: the influence of stereo-defects, Eindhoven: Technische Universiteit Eindhoven, 2002.
• [21] R.T. Sanderson, “Principle of electronegativity. Part I. General nature,” J. Chem. Educ. Soc., vol. 65(2), pp. 112-118, 1988.
• [22] T. Chakraborty, K. Gazi, and D.C. Ghosh, “Computation of the atomic radii through the conjoint action of the effective nuclear charge and the ionization energy,” Mol. Phys., vol. 108(16), pp. 2081-2092, 2010.