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Phase Behavior of Selected Condensed Double-Decker Shaped Silsesquioxane Compounds

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Abstract

Bisfunctional dichlorosilanes were reacted with tetrasilanol of double-decker shaped octaphenylsilsesquioxane (DDSQ) to form fully condensed DDSQ compounds. The crystallographic and thermal characteristics of these compounds were examined. For compounds capped with dichlorosilanes bearing linear aliphatic moieties, as the number of carbon increases from methyl to n-butyl (from 1 to 4) the melting temperature, Tm, dropped from 546 K to 416 K. While for compounds capped with cycloaliphatic, as the moiety changes from cyclopentyl to cyclohexyl, the value of Tm increases from 533 K to 555 K. Surprising, the highest Tm observed was that when capping was done using diisopropyl dichlorosilane. A Tm of around 565 K was observed, which was even higher as compare to diphenyl dichlorosilane capped DDSQ, which had Tm of about 526 K. Phase behavior of binary and ternary mixtures of these condensed DDSQ was also investigated. To our surprise, mixtures of these compounds form eutectic. The eutectic points were calculated based on ideal binary and ternary eutectic from the thermal properties of pure components. Depending on the crystallography, experimental observations of eutectic match well with calculated values.

Graphical abstract

Melting and evaporation temperatures were identified for functionalized double-decker shaped silsesquioxanes, melting temperature suppression was observed after mixing DDSQ with different functional groups.

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Data Availability

Materials and equipment used for this work are described within the manuscript. In addition, experimental details, spectral information, crystal structures, DSC traces, and phase diagrams are also provided in supplementary information.

References

  1. Schoen BW, Holmes D, Lee A (2013) Identification and quantification of cis and trans isomers in aminophenyl double-decker silsesquioxanes using 1H-29Si gHMBC NMR. Magn Reson Chem 51:490–496. https://doi.org/10.1002/mrc.3962

    Article  CAS  PubMed  Google Scholar 

  2. Schoen BW, Lira CT, Lee A (2014) Separation and solubility of Cis and trans isomers in nanostructured double-Decker Silsequioxanes. J Chem Eng Data 59:1483–1493. https://doi.org/10.1021/je4010245

    Article  CAS  Google Scholar 

  3. Seurer B, Vij V, Haddad T, Mabry JM, Lee A (2010) Thermal transitions and reaction kinetics of Polyhederal Silsesquioxane containing Phenylethynylphthalimides. Macromolecules 43:9337–9347. https://doi.org/10.1021/ma101640q

    Article  CAS  Google Scholar 

  4. Moore LMJ, Zavala JJ, Lamb JT, Reams JT, Yandek GR, Guenthner AJ, Haddad TS, Ghiassi KB (2018) Bis-phenylethynyl polyhedral oligomeric silsesquioxanes: new high-temperature, processable thermosetting materials. RSC Adv 8:27400–27405. https://doi.org/10.1039/C8RA05954C

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Hoque MA, Kakihana Y, Shinke S, Kawakami Y (2009) Polysiloxanes with periodically distributed isomeric double-Decker Silsesquioxane in the Main chain. Macromolecules 42:3309–3315. https://doi.org/10.1021/ma900124x

    Article  CAS  Google Scholar 

  6. Wei K, Wang L, Zheng S (2013) Organic–inorganic polyurethanes with 3,13-dihydroxypropyloctaphenyl double-decker silsesquioxane chain extender. Polym Chem 4:1491–1501. https://doi.org/10.1039/C2PY20930F

    Article  CAS  Google Scholar 

  7. Tanaka T, Hasegawa Y, Kawamori T, Kunthom R, Takeda N, Unno M (2019) Synthesis of double-Decker Silsesquioxanes from substituted Difluorosilane. Organometallics 38:743–747. https://doi.org/10.1021/acs.organomet.8b00896

    Article  CAS  Google Scholar 

  8. Mituła K, Dudziec B, Marciniec B (2018) Synthesis of Dialkenyl-substituted double-Decker Silsesquioxanes as precursors for linear Copolymeric systems. J Inorg Organomet Polym Mater 28:500–507. https://doi.org/10.1007/s10904-017-0746-y

    Article  CAS  Google Scholar 

  9. Walczak M, Januszewski R, Majchrzak M, Kubicki M, Dudziec B, Marciniec B (2017) Unusual cis and trans architecture of dihydrofunctional double-decker shaped silsesquioxane and synthesis of its ethyl bridged π-conjugated arene derivatives. New J Chem 41:3290–3296. https://doi.org/10.1039/C7NJ00255F

    Article  CAS  Google Scholar 

  10. Żak P, Dudziec B, Dutkiewicz M, Ludwiczak M, Marciniec B, Nowicki M (2016) A new class of stereoregular vinylene-arylene copolymers with double-decker silsesquioxane in the main chain. J Polym Sci Part A: Polym Chem 54:1044–1055. https://doi.org/10.1002/pola.27957

    Article  CAS  Google Scholar 

  11. Wang M, Chi H, KS J, Wang F (2019) Progress in the synthesis of Bifunctionalized polyhedral oligomeric Silsesquioxane. Polymers 11:2098. https://doi.org/10.3390/polym11122098

    Article  CAS  PubMed Central  Google Scholar 

  12. Beata D, Bogdan M (2017) Double-decker silsesquioxanes: current chemistry and applications. Curr Org Chem 21:2794–2813

    Google Scholar 

  13. Cao J, Fan H, Li B-G, Zhu S (2017) Synthesis and evaluation of double-Decker Silsesquioxanes as modifying agent for epoxy resin. Polymer 124:157–167. https://doi.org/10.1016/j.polymer.2017.07.056

    Article  CAS  Google Scholar 

  14. Xu S, Zhao B, Wei K, Zheng S (2018) Organic-inorganic polyurethanes with double decker silsesquioxanes in the main chains: morphologies, surface hydrophobicity, and shape memory properties. J Polym Sci B Polym Phys 56:893–906. https://doi.org/10.1002/polb.24603

    Article  CAS  Google Scholar 

  15. Liu N, Wei K, Wang L, Zheng S (2016) Organic–inorganic polyimides with double decker silsesquioxane in the main chains. Polym Chem 7:1158–1167. https://doi.org/10.1039/c5py01827g

    Article  CAS  Google Scholar 

  16. Liu N, Li L, Wang L, Zheng S (2017) Organic-inorganic polybenzoxazine copolymers with double decker silsesquioxanes in the main chains: synthesis and thermally activated ring-opening polymerization behavior. Polymer 109:254–265. https://doi.org/10.1016/j.polymer.2016.12.049

    Article  CAS  Google Scholar 

  17. Wu S, Hayakawa T, Kakimoto M-A, Oikawa H (2008) Synthesis and characterization of Organosoluble aromatic polyimides containing POSS in Main chain derived from double-Decker-shaped Silsesquioxane. Macromolecules 41:3481–3487. https://doi.org/10.1021/ma7027227

    Article  CAS  Google Scholar 

  18. Jiang Q, Zhang W, Hao J, Wei Y, Mu J, Jiang Z (2015) A unique “cage–cage” shaped hydrophobic fluoropolymer film derived from a novel double-decker structural POSS with a low dielectric constant. J Mater Chem 3:11729–11734. https://doi.org/10.1039/C5TC02432C

    Article  CAS  Google Scholar 

  19. Wang Z, Yonggang L, Huijuan M, Wenpeng S, Tao L, Cuifen L, Junqi N, Guichun Y, Zuxing C (2018) Novel phosphorus-nitrogen-silicon copolymers with double-decker silsesquioxane in the main chain and their flame retardancy application in PC/ABS. Fire Mater 2:16230–16957. https://doi.org/10.1002/fam.2649

    Article  CAS  Google Scholar 

  20. Vogelsang DF, Maleczka RE, Lee A (2019) Predictive liquid chromatography separation for mixtures of functionalized double-Decker shaped Silsesquioxanes based on HPLC chromatograms. Ind Eng Chem Res 58:403–410. https://doi.org/10.1021/acs.iecr.8b05490

    Article  CAS  Google Scholar 

  21. Vogelsang DF, Dannatt JE, Schoen BW (2019) Phase behavior of cis-trans mixtures of double-decker shaped Silsesquioxanes for Processability enhancement. ACS App Nano 2:1223–1231. https://doi.org/10.1021/acsanm.8b02114

    Article  CAS  Google Scholar 

  22. Vogelsang DF, Maleczka RE, Lee A (2019) HPLC characterization of cis and trans mixtures of double-Decker shaped Silsesquioxanes. Silicon Chem 11:5–13. https://doi.org/10.1007/s12633-018-0045-4

    Article  CAS  Google Scholar 

  23. Clavaguera N, Saurina J, Lheritier J, Masse J, Chauvet A, Clavaguera-Mora MT (1997) Eutectic mixtures for pharmaceutical applications: a thermodynamic and kinetic study. Thermochim Acta 290:173–180. https://doi.org/10.1016/S0040-6031(96)03077-8

    Article  CAS  Google Scholar 

  24. Fiala S, Brown MB, Jones SA (2011) Dynamic in-situ eutectic formation for topical drug delivery. J Pharm Pharmacol 63:1428–1436

    Article  CAS  Google Scholar 

  25. Lee A, Lu Y, Roche A, Pan T-Y (2016) Influence of Nano-structured Silanols on the microstructure and mechanical properties of A4047 and A359 aluminum casting alloys. Int J Met 10:338–341. https://doi.org/10.1007/s40962-016-0044-4

    Article  Google Scholar 

  26. Liu S, Ma L, Shu Y, Subramanian KN, Lee A, Guo F (2014) Effects of POSS-Silanol addition on whisker formation in Sn-based Pb-free electronic solders. J Electron Mater 43:26–32. https://doi.org/10.1007/s11664-013-2672-2

    Article  CAS  Google Scholar 

  27. Brostow W, Goodman SH, Wahrmund J (2013) In: Dodiuk H and Goodman SH (ed) Handbook of Thermoset Plastics, 3rd edn. Elsevier, Oxford, UK

  28. Fina A, Tabuani D, Carniato F, Frache A, Boccaleri E, Camino G (2006) Polyhedral oligomeric silsesquioxanes (POSS) thermal degradation. Thermochim Acta 440:36–42. https://doi.org/10.1016/j.tca.2005.10.006

    Article  CAS  Google Scholar 

  29. Blanco I, Abate L, Bottino FA (2017) Mono substituted octaphenyl POSSs: the effects of substituents on thermal properties and solubility. Thermochim Acta 655:117–123. https://doi.org/10.1016/j.tca.2017.06.019

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Authors are grateful to Drs. Daniel Holmes, Richard Staples and Ms. Emily Dong for their support of NMR, X-ray crystallography and DSC studies, respectively. Additionally, Dr. Jairo Perilla from Universidad Nacional of Colombia for his collaboration and valuable discussion.

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Funding

This work was partially supported by the Office of Naval Research (N00014–16-2109) for generous funding.

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Authors and Affiliations

  1. Department of Chemical Engineering and Materials Science, Michigan State University, 428 S. Shaw Lane, Room 2100, East Lansing, MI, 48824-1226, USA

    David F. Vogelsang & Andre Lee

  2. Department of Chemistry, Michigan State University, 578 S. Shaw Lane, East Lansing, MI, 48824-1322, USA

    Robert E. Maleczka Jr

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  1. David F. Vogelsang
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  2. Robert E. Maleczka Jr
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Correspondence to Robert E. Maleczka Jr or Andre Lee.

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Vogelsang, D.F., Maleczka, R.E. & Lee, A. Phase Behavior of Selected Condensed Double-Decker Shaped Silsesquioxane Compounds. Silicon 14, 7555–7565 (2022). https://doi.org/10.1007/s12633-021-01470-0

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