Synthesis and Molecular Dynamics Simulation of Isooctyltriethoxysilane and Its Lithium Salt Compounds

ZHAO He-yi; LIANG Jia-xiang; YANG Rong-jie

doi:10.14028/j.cnki.1003-3726.2026.25.317

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Synthesis and Molecular Dynamics Simulation of Isooctyltriethoxysilane and Its Lithium Salt Compounds

更新时间：2026-04-30

- Synthesis and Molecular Dynamics Simulation of Isooctyltriethoxysilane and Its Lithium Salt Compounds
- Polymer Bulletin Vol. 39, Issue 5, Pages: 764-773(2026)
- 作者机构：
  
  北京理工大学材料学院国家阻燃材料工程技术研究中心　北京 100081
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2026.25.317
  CLC：
- Received：03 November 2025，
  
  Accepted：26 February 2026，
  
  Online First：09 April 2026，
  
  Published：20 May 2026
- 稿件说明：
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赵贺一, 梁嘉香, 杨荣杰. 七异辛基三羟基硅倍半氧烷及其锂盐的合成表征与分子动力学模拟. 高分子通报, 2026, 39(5), 764–773.

Zhao, H. Y.; Liang, J. X.; Yang, R. J. Synthesis and molecular dynamics simulation of isooctyltriethoxysilane and its lithium salt compounds. Polym. Bull. (in Chinese), 2026, 39(5), 764–773.
赵贺一, 梁嘉香, 杨荣杰. 七异辛基三羟基硅倍半氧烷及其锂盐的合成表征与分子动力学模拟. 高分子通报, 2026, 39(5), 764–773. DOI： 10.14028/j.cnki.1003-3726.2026.25.317.

Zhao, H. Y.; Liang, J. X.; Yang, R. J. Synthesis and molecular dynamics simulation of isooctyltriethoxysilane and its lithium salt compounds. Polym. Bull. (in Chinese), 2026, 39(5), 764–773. DOI： 10.14028/j.cnki.1003-3726.2026.25.317.

摘要

高产率高纯度地制备了七异辛基三羟基硅倍半氧烷(iO-T

)及其锂盐(iO-T

-OLi)。通过傅里叶变换红外光谱(FTIR)、核磁共振(NMR)和基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)多种手段对产物结构进行了系统表征，确认iO-T

-OLi为锂盐二取代结构，拓展了不完全缩合POSS的结构类型。采用示差扫描量热分析(DSC)测定了iO-T

和iO-T

-OLi的玻璃化转变温度(

)，在10 K/min的升温速率下分别为244.05和239.35 K，采用分子动力学(MD)模拟的iO-T

和iO-T

-OLi的

则分别为225.87和216.45 K，揭示了iO-T

和iO-T

-OLi的玻璃化转变行为。计算了iO-T

和iO-T

-OLi的径向分布函数，从分子间相互作用及链运动方面进行了详细分析。

Abstract

Isooctyltriethoxysilane (iO-T

) and its lithium salt compounds (iO-T

-OLi) were prepared with high yield and high purity. The structures of the products were systematically characterized using diverse methods

including Fourier transform infrared spectroscopy (FTIR)

nuclear magnetic resonance spectroscopy (

H-NMR

C-NMR

Si-NMR)

and MALDI-TOF MS. It was confirmed that iO-T

-OLi possesses a disubstituted lithium salt structure

thereby expanding the structural diversity of incompletely condensed POSS. The glass transition temperatures (

) of iO-T

and iO-T

-OLi were determined via differential scanning calorimetry (DSC) at a heating rate of 10 K/min

yielding values of 244.05 and 239.35 K

respectively. Additionally

the

values derived from molecular dynamics (MD) simulations were 225.87 and 216.45 K

respectively

providing insights into the glass transition behaviors of the compounds. Furthermore

radial distribution functions for both iO-T

and iO-T

-OLi were calculated

and a detailed analysis was performed considering intermolecular interactions and chain dynamics.

关键词

Keywords

references

DeArmitt, C . Polyhedral oligomeric silsesquioxanes in plastics . Dordrecht : Springer Netherlands , 2011 . 209 – 228 .

Baney, R. H. ; Itoh, M. ; Sakakibara, A. ; Suzuki, T . Silsesquioxanes . Chem. Rev. , 1995 , 95 ( 5 ), 1409 – 1430 .

Kuo, S. W. ; Chang, F. C . POSS related polymer nanocom-posites . Prog. Polym. Sci. , 2011 , 36 ( 12 ), 1649 – 1696 .

Zhang, W. C. ; Camino, G. ; Yang, R. J . Polymer/polyhedral oligomeric silsesquioxane (POSS) nano-composites: an overview of fire retardance . Prog. Polym. Sci. , 2017 , 67 , 77 – 125 .

Mabry, J. ; Vij, A. ; Iacono, S. ; Viers, B . Fluorinated polyhedral oligomeric silsesquioxanes (F-POSS) . Angew. Chem. Int. Ed. , 2008 , 47 ( 22 ), 4137 – 4140 .

Marcolli, C. ; Calzaferri, G . Monosubstituted octasilasesquioxanes . Appl. Organomet. Chem. , 1999 , 13 ( 4 ), 213 – 226 .

Tanaka, K. ; Chujo, Y . Advanced functional materials based on polyhedral oligomeric silsesquioxane (POSS) . J. Mater. Chem. , 2012 , 22 ( 5 ), 1733 – 1746 .

Brząkalski, D. ; Przekop, R. E. ; Sztorch, B. ; Jakubowska, P. ; Jałbrzykowski, M. ; Marciniec, B . Silsesquioxane derivatives as functional additives for preparation of polyethylene-based composites: a case of trisilanol melt-condensation . Polymers , 2020 , 12 ( 10 ), 2269 .

Ye, X. M. ; Li, J. J. ; Zhang, W. C. ; Yang, R. J. ; Li, J. R . Fabrication of eco-friendly and multifunctional sodium-containing polyhedral oligomeric silsesquioxane and its flame retardancy on epoxy resin . Compos. Part B Eng. , 2020 , 191 , 107961 .

Ye, X. M. ; Zhang, W. C. ; Yang, R. J. ; He, J. Y. ; Li, J. R. ; Zhao, F. Q . Facile synthesis of lithium containing polyhedral oligomeric phenyl silsesquioxane and its superior performance in transparency, smoke suppression and flame retardancy of epoxy resin . Compos. Sci. Technol. , 2020 , 189 , 108004 .

Wheeler, P. A. ; Misra, R. ; Cook, R. D. ; Morgan, S. E . Polyhedral oligomeric silsesquioxane trisilanols as dispersants for titanium oxide nanopowder . J. Appl. Polym. Sci. , 2008 , 108 ( 4 ), 2503 – 2508 .

Conradi, M. ; Kocijan, A. ; Kek-Merl, D. ; Zorko, M. ; Verpoest, I . Mechanical and anticorrosion properties of nanosilica-filled epoxy-resin composite coatings . Appl. Surf. Sci. , 2014 , 292 , 432 – 437 .

Ye, Y. W. ; Yang, D. P. ; Zhang, D. W. ; Chen, H. ; Zhao, H. C. ; Li, X. G. ; Wang, L. P . POSS-tetraaniline modified graphene for active corrosion protection of epoxy-based organic coating . Chem. Eng. J. , 2020 , 383 , 123160 .

Wang, J. ; Ali Zaidi, S. S. ; Hasnain, A. ; Guo, J. T. ; Ren, X. K. ; Xia, S. H. ; Zhang, W. C. ; Feng, Y. K . Multitargeting peptide-functionalized star-shaped copolymers with comblike structure and a POSS-core to effectively transfect endothelial cells . ACS Biomater. Sci. Eng. , 2018 , 4 ( 6 ), 2155 – 2168 .

Ghani, K. ; Keshavarz, M. H. ; Jafari, M. ; Khademian, F . A novel method for predicting decomposition onset temperature of cubic polyhedral oligomeric silsesquioxane derivatives . J. Therm. Anal. Calorim. , 2018 , 132 ( 1 ), 761 – 770 .

刘昊东 , 朱光明 , 任天宁 . 功能性POSS制备的研究进展 . 材料工程 , 2019 , 47 ( 12 ), 33 – 42 .

Feher, F. J. ; Budzichowski, T. A. ; Blanski, R. L. ; Weller, K. J. ; Ziller, J. W . Facile syntheses of new incom-pletely condensed polyhedral oligosilsesquioxanes: (c-C 5 H 9 ) 7 Si 7 O 9 (OH) 3 , (c-C 7 H 13 ) 7 Si 7 O 9 (OH) 3 , and (c-C 7 H 13 ) 6 Si 6 O 7 (OH) 4 . Organometallics , 1991 , 10 ( 7 ), 2526 – 2528 .

Feher, F. J. ; Newman, D. A. ; Walzer, J. F . Silsesquioxanes as models for silica surfaces . J. Am. Chem. Soc. , 1989 , 111 ( 5 ), 1741 – 1748 .

Innocenzi, P. ; Figus, C. ; Kidchob, T. ; Valentini, M. ; Alonso, B. ; Takahashi, M . Sol-gel reactions of 3-glycidoxypropyltrimethoxysilane in a highly basic aqueous solution . Dalton Trans. , 2009 ( 42 ), 9146 – 9152 .

Zhou, J. L. ; Zhao, Y. C. ; Yu, K. C. ; Zhou, X. P. ; Xie, X. L . Synthesis, thermal stability and photoresponsive behaviors of azobenzene-tethered polyhedral oligomeric silsesquioxanes . New J. Chem. , 2011 , 35 ( 12 ), 2781 – 2792 .

Fina, A. ; Abbenhuis, H. C. L. ; Tabuani, D. ; Frache, A. ; Camino, G . Polypropylene metal functionalised POSS nanocomposites: a study by thermogravimetric analysis . Polym. Degrad. Stab. , 2006 , 91 ( 5 ), 1064 – 1070 .

Carniato, F. ; Bisio, C. ; Boccaleri, E. ; Guidotti, M. ; Gavrilova, E. ; Marchese, L . Titanosilsesquioxane anchored on mesoporous silicas: a novel approach for the preparation of heterogeneous catalysts for selective oxidations . Chem. , 2008 , 14 ( 27 ), 8098 – 8101 .

Wang, Y. M. ; Magusin, P. C. M. M. ; van Santen, R. A. ; Abbenhuis, H. C. L . Organo-bridged silsesquioxane titanates for heterogeneous catalytic epoxidation with aqueous hydrogen peroxide . J. Catal. , 2007 , 251 ( 2 ), 453 – 458 .

Monticelli, O. ; Zunino, E. ; Carniato, F. ; Boccaleri, E. ; Marchese, L. ; Chincarini, A . Novel polymer nanocomposites based on polystyrene and Ti-functionalized polyhedral silsesquioxanes . Polym. Adv. Technol. , 2010 , 21 ( 12 ), 848 – 853 .

Lee, D. W. ; Kawakami, Y . Incompletely condensed silsesquioxanes: formation and reactivity . Polym. J. , 2007 , 39 ( 3 ), 230 – 238 .

Ye, X. M. ; Zhang, X. L. ; Jiang, Y. Y. ; Qiao, L. ; Zhang, W. C. ; Pan, Y. T. ; Yang, R. J. ; Li, J. R. ; Li, Y. C . Controllable dimensions and regular geometric architectures from self-assembly of lithium-containing polyhedral oligomeric silsesquioxane: build for enhancing the fire safety of epoxy resin . Compos. Part B Eng. , 2022 , 229 , 109483 .

Ye, M. F. ; Wu, Y. W. ; Zhang, W. C. ; Yang, R. J . Synthesis of incompletely caged silsesquioxane (T 7 -POSS) compounds via a versatile three-step approach . Res. Chem. Intermed. , 2018 , 44 ( 7 ), 4277 – 4294 .

Fiorio, R. ; Danda, C. ; Maia, J . Influence of trisilanol isooctyl POSS content on the structure, morphology and rheological properties of thermoplastic polyurethane (TPU) . J. Polym. Eng. , 2020 , 40 ( 9 ), 727 – 735 .

Fiorio, R. ; Pistor, V. ; Zattera, A. J. ; Petzhold, C. L . Polymerization kinetics of polyurethanes containing trisilanol isooctyl polyhedral oligomeric silsesquioxane . J. Elastomers Plast. , 2014 , 46 ( 7 ), 594 – 610 .

Mihelčič, M. ; Gaberšček, M. ; Salzano de Luna, M. ; Lavorgna, M. ; Giuliani, C. ; Di Carlo, G. ; Surca, A. K . Effect of silsesquioxane addition on the protective performance of fluoropolymer coatings for bronze surfaces . Mater. Des. , 2019 , 178 , 107860 .

Mihelčič, M. ; Gaberšček, M. ; Di Carlo, G. ; Giuliani, C. ; Salzano de Luna, M. ; Lavorgna, M. ; Surca, A. K . Influence of silsesquioxane addition on polyurethane-based protective coatings for bronze surfaces . Appl. Surf. Sci. , 2019 , 467 – 468, 912–925 .

Lichtenhan, J. D. ; Hildebrandt, D. A. ; Lancaster, L. J . The thrombogenic activity of POSS silanols . Dalton Trans. , 2017 , 46 ( 27 ), 8788 – 8796 .

Krasowska, A. ; Sigler, K . How microorganisms use hydrophobicity and what does this mean for human needs Front . Cell. Infect. Microbiol. , 2014 , 4 , 112 .

Brown, C. ; Groves, M. ; Ivory, Y. ; Anderson, P. ; Tucci, M. ; Cason, Z . Early effects of POSS on tissue healing using a pig model . J. Miss. Acad. Sci. , 2013 , 58 ( 4 ), 214 – 218 .

Feher, F. J. ; Budzichowski, T. A. ; Weller, K. J . Polyhedral aluminosilsesquioxanes: soluble organic analogs of aluminosilicates . J. Am. Chem. Soc. , 1989 , 111 ( 18 ), 7288 – 7289 .

Plimpton, S . Fast parallel algorithms for short-range molecular dynamics . J. Comput. Phys. , 1995 , 117 ( 1 ), 1 – 19 .

Sun, H. ; Jin, Z. ; Yang, C. W. ; Akkermans, R. L. C. ; Robertson, S. H. ; Spenley, N. A. ; Miller, S. ; Todd, S. M . COMPASS II: Extended coverage for polymer and drug-like molecule databases . J. Mol. Model. , 2016 , 22 ( 2 ), 47 .

Grunina, N. A. ; Belopolskaya, T. V. ; Tsereteli, G. I . The glass transition process in humid biopolymers . DSC study. J. Phys. Conf. Ser. , 2006 , 40 ( 1 ), 105 .

Allen, M. P. ; Tildesley, D. J . Computer Simulation of Liquids . Oxford : Oxford University Press , 2017 . 95 – 146 .

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