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Thermal Aspects of Kumada Rearrangement in Symmetrical and Asymmetrical Polysilanes-Interdependence of Molecular Structure, Thermal Degradation, and Stability

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Abstract

Thermal degradation behavior, exothermic patterns, and kinetic parameters of symmetrically/asymmetrically substituted polysilanes during the kumada thermal rearrangement in the temperature range of 100–450 °C, were investigated applying thermogravimetric (TGA) and differential scanning calorimetric (DSC) techniques. Three kinds of polysilanes, viz., Polydimethylsilane (PDMS), Polydiphenylsilane (PDPS) and Polymethylphenylsilane (PMPS) were synthesized through Wurtz/Wurtz-Fittig polycondensation. As-synthesized polysilanes were then characterized by FT-IR, CHNO, and TGA–DSC techniques. FT-IR spectra confirmed the presence of methyl, phenyl, and a combination of methyl-phenyl functional groups in PDMS, PDPS, and PMPS, respectively. From CHNO analysis, the chemical/empirical formula of PDMS, PDPS, and PMPS was found to be SiC2.01H6.25, SiC12.50H10.26, and SiC6.45H7.76, respectively. TGA results confirmed that PDPS was more thermally stable as compared to PDMS and PMPS. The kinetic parameters of polysilanes were determined by using isoconversional methods such as Ozawa and modified Kissinger–Akahira–Sunose (KAS) methods. The average value of activation energy for PDPS obtained from Ozawa and KAS methods was found to be 1078.49 and 1068.32 kJ/mole, respectively, which is very much higher as compared to that of PDMS and PMPS.

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References

  1. Miller RD, Michl J (1989) Polysilane high polymers. Chem Rev 89:1359–1410. https://doi.org/10.1021/cr00096a006

    Article  CAS  Google Scholar 

  2. Kyushin S, Ichikawa K, Koyama Y, Shiraiwa H, Ichikawa H, Okamura K, Suzuki K (2014) Studies on the detailed structure of poly(dimethylsilylene). Organometallics 33:6298–6304. https://doi.org/10.1021/om500264u

    Article  CAS  Google Scholar 

  3. West R (1986) The polysilane high polymers. J Organometal Chem 300:327–346. https://doi.org/10.1016/0022-328X(86)84068-2

    Article  CAS  Google Scholar 

  4. Trefonas P, West R, Miller RD (1985) Polysilane high polymers: mechanism of photodegradation. J Am Chem Soc 107:2737–2742. https://doi.org/10.1021/ja00295a028

    Article  CAS  Google Scholar 

  5. Tverdokhlebova II, Ronova IA, Men’shov VM, Pertsova NV (1998) Molecular architecture and conformation of macromolecules of novel polysilanes. Russ Chem Bull 4:2348–2351. https://doi.org/10.1007/BF02641532

    Article  Google Scholar 

  6. Grabe N, Michael Rothmann (2017) Method for the synthesis of a chlorine-free, pre-ceramic polymer for the production of ceramic molded bodies. U.S. Patent 9,644,073

  7. Li GY, Li XD, Wang H, Liu L (2010) Long SiC nanowires synthesized from off-gases of the polycarbosilane-derived SiC preparation. Appl Phy 98:293. https://doi.org/10.1007/s00339-009-5426-5

    Article  CAS  Google Scholar 

  8. Burkhard AC (1949) Polydimethylsilanes. J Am Chem Soc 71:963–964. https://doi.org/10.1021/ja01171a055

    Article  CAS  Google Scholar 

  9. Miller RD, Sooriyakumaran R (1987) The synthesis and characterization of the first soluble, high molecular weight, substituted poly (diphenyl silane) homopolymer. J Polym Sci Part C: Polym Lett 25:321–326. https://doi.org/10.1002/pol.1987.140250803

    Article  CAS  Google Scholar 

  10. Lodhe M, Narendra B, Selvam A, Balasubramanian M (2015) Synthesis and characterization of high ceramic yield polycarbosilane precursor for SiC. J Adv Cer 4:307–311. https://doi.org/10.1007/s40145-015-0165-x

    Article  CAS  Google Scholar 

  11. Yajima S, Hasegawa Y, Okamura K, Matsuzawa T (1978) Development of high tensile strength silicon carbide fiber using an organosilicon polymer precursor. Nature 273:525–527. https://doi.org/10.1038/273525a0

    Article  CAS  Google Scholar 

  12. Noda K, Takehiro S, Issei S, Kouichi M, Dai S, Shun K, Masahiro F, Koji A (2018) Behavior of Si-Si Bond Oxidation by Electron Beam Lithography. J Photopoly Sci Tech 31:581–585. https://doi.org/10.2494/photopolymer.31.581

    Article  CAS  Google Scholar 

  13. Cypryk M, Yogendra G, Krzysztof M (1991) Anionic ring-opening polymerization of 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-tetraphenylcyclotetrasilane. J Ame Chem Soc 113:1046–1047. https://doi.org/10.1021/ja00003a050

    Article  CAS  Google Scholar 

  14. Jones RG, Ulrich B, Simon JH, William KC (1996) Reappraisal of the origins of the polymodal molecular mass distributions in the formation of poly (methylphenylsilylene) by the Wurtz reductive-coupling reaction. Macromol 29:8036–8046. https://doi.org/10.1021/ma960496y

    Article  CAS  Google Scholar 

  15. Kipping FS, James ES (1921) XCIII.—Organic derivatives of silicon. Part XXV. Saturated and unsaturated silicohydrocarbons Si4Ph8. J Chem Soc Trans 119:830–847. https://doi.org/10.1039/CT9211900830

    Article  CAS  Google Scholar 

  16. Kipping FS (1924) CCCVIII. —Organic derivatives of silicon. Part XXX. Complex silicohydrocarbons [SiPh2]n. J Chem Soc Trans 125:2291–2297. https://doi.org/10.1039/CT9242502291

    Article  CAS  Google Scholar 

  17. Mavric A, Artem B, Mattia F, Matjaz V (2016) Molecular size and solubility conditions of polysilane macromolecules with different topology. Sci Rep 6:1–8. https://doi.org/10.1038/srep35450

    Article  CAS  Google Scholar 

  18. Abu-eid MA, King RB, Kotliar AM (1992) Synthesis of polysilane polymer precursors and their pyrolysis to silicon carbides. Eur Polym J 28:315–320. https://doi.org/10.1016/0014-3057(92)90196-9

    Article  CAS  Google Scholar 

  19. Lee YJ, Lee JH, Kim SR, Kwon WT, Oh H, Klepeis JH, Teat SJ, Kim YH (2010) Synthesis and characterization of novel pre-ceramic polymer for SiC. J Mater Sci 45:1025–1031. https://doi.org/10.1007/s10853-009-4034-2

    Article  CAS  Google Scholar 

  20. Watanabe A, Komatsubara T, Matsuda M, Yoshida Y, Tagawa S (1995) Radical ions of poly(phenylsilyne) and poly(phenylgermyne). Macromol Chem Phys 1101:1229–1240. https://doi.org/10.1002/macp.1995.021960422

    Article  Google Scholar 

  21. Yoshikawa M, Goshi Y, Yamada S, Koga N (2014) Multistep kinetic behavior in the thermal degradation of poly (L-lactic acid): a physico-geometrical kinetic interpretation. J Phys Chem B 118:11397–11405. https://doi.org/10.1021/jp507247x

    Article  CAS  PubMed  Google Scholar 

  22. Dong F, Sun X, Feng S (2016) Thermal degradation kinetics of functional polysiloxanes containing chloromethyl groups. Thermochim Acta 639:14–19. https://doi.org/10.1016/j.tca.2016.07.007

    Article  CAS  Google Scholar 

  23. Li L, Wei G, Bin L, Jia-Jia J, Jun-Cheng J, Chi-Min S (2021) Effects of 1-butyl-3-metylimidazolium tetrafluoroborate on the thermal hazard of triacetone triperoxide. Process Saf Environ Prot 149:518–525. https://doi.org/10.1016/j.psep.2020.11.008

    Article  CAS  Google Scholar 

  24. Santhana Krishnan G, Naveen S, Shahnawaz M, Ramcharan T (2022) Pyrolysis and thermal degradation studies of silane-carbosilane transformation using hyphenated thermal analysis. J Anal Appl Pyrolysis 164:105535. https://doi.org/10.1016/j.jaap.2022.105535

    Article  CAS  Google Scholar 

  25. Shukla SK, Tiwari RK, Ranjan A, Saxena AK, Mathur GN (2004) Some thermal studies on Polysilanes and Polycarbosilanes. Thermochim Acta 424:209–217. https://doi.org/10.1016/j.tca.2004.06.003

    Article  CAS  Google Scholar 

  26. Vyazovkin S, Burnham AK, Criado JM, Pérez-Maqueda LA, Popescu C, Sbirrazzuoli N (2011) ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta 520:1–19. https://doi.org/10.1016/j.tca.2011.03.034

    Article  CAS  Google Scholar 

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Acknowledgements

The research work was carried out as part of the project under the development of functional ceramic polymer precursors (Grant No M-8-116). Financial support by CSIR-National Aerospace Laboratories, Bangalore, India, is gratefully acknowledged. Authors thank the Director and Head, Materials Science Division, CSIR-National Aerospace Laboratories, Bangalore, for their support and permission to publish this work.

Funding

The research work was carried out as part of the project under the development of functional ceramic polymer precursors (Grant No M-8–116).

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Authors and Affiliations

  1. Materials Science Division, CSIR-National Aerospace Laboratories, Bangalore, 560017, India

    G. Santhana Krishnan & M. Shahnawaz

  2. School of Materials Science and Engineering, National Institute of Technology, Calicut, India

    T. Ramcharan

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  1. G. Santhana Krishnan
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  2. M. Shahnawaz
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  3. T. Ramcharan
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Contributions

All authors contributed to the study conception and design of experiment, polymer synthesis experiments, sample preparation for thermal and spectral characterization, data collection [Shahnawaz, M. and Ramcharan,T] The first draft of the manuscript was written by G Santhana Krishnan and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to G. Santhana Krishnan.

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Santhana Krishnan, G., Shahnawaz, M. & Ramcharan, T. Thermal Aspects of Kumada Rearrangement in Symmetrical and Asymmetrical Polysilanes-Interdependence of Molecular Structure, Thermal Degradation, and Stability. Silicon 15, 1499–1510 (2023). https://doi.org/10.1007/s12633-022-02126-3

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