Abstract
A series of necklace-shaped alternating siloxane copolymers that consisted of a bifunctional polyhedral oligomeric silsesquioxane (POSS) cage and flexible linear dimethyloligosiloxane (DMS) chain segment have been synthesized from bifunctional POSS molecules by two different synthetic methodologies, polycon-densation and ring-opening polymerization. Necklace-shaped POSS-DMS polymers with three different chain arrangements, “constant chain,” “random chain,” and “alternating modulated chain,” have been synthesized. The necklace-shaped POSS-DMS polymers gave transparent thermoplastic and thermosetting plastics with high heat resistance upon cross-linking at the end of the polymers. The controllable structural diversity of these polymers allows control of their physical properties such as flexibility and glass transition temperature. These necklace-shaped polymers consisting of bulky functional inorganic units and alternately connected short soft chains will pave the way to inorganic soft materials, which are novel inorganic materials that can be handled like an organic polymer possessing solubility, plasticity, or entropic elasticity.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Chujo Y, Tanaka K (2015) New polymeric materials based on element-blocks. Bull Chem Soc Jpn 88:633–643. https://doi.org/10.1246/bcsj.20150081
Kuo SW, Chang FC (2011) POSS related polymer nanocomposites. Prog Polym Sci 36:1649–1696. https://doi.org/10.1016/j.progpolymsci.2011.05.002
Han S-Y, Wang X-M, Shao Y, Guo Q-Y, Li Y, Zhang W-B (2016) Janus POSS based on mixed [2:6] octakis-adduct regioisomers. Chem A Eur J 22:6397–6403. https://doi.org/10.1002/chem.201600579
Li G, Charles UP (2005) Polyhedral oligomeric silsesquioxane (POSS) polymers, copolymers, and resin nanocomposites. Macromol Contain Met Met Elem Gr IVA Polym 4:79–131. https://doi.org/10.1002/0471712566.ch5
Laine RM, Roll MF (2011) Polyhedral phenylsilsesquioxanes. Macromolecules 44:1073–1109. https://doi.org/10.1021/ma102360t
Araki H, Naka K (2012) Syntheses and properties of star- and dumbbell-shaped POSS derivatives containing isobutyl groups. J Polym Sci Part A 50:4170–4181
Zhang W, Camino G, Yang R (2016) Polymer/polyhedral oligomeric silsesquioxane (POSS) nanocomposites: an overview of fire retardance. Prog Polym Sci 67:77–125. https://doi.org/10.1016/j.progpolymsci.2016.09.011
Katsuta N, Yoshimatsu M, Komori K, Natsuaki T, Suwa K, Sakai K, Matsuo T, Ohba T, Uemura S, Watanabe S, Kunitake M (2017) Necklace-shaped dimethylsiloxane polymers bearing polyhedral oligomeric silsesquioxane cages with alternating length chains. Polym (United Kingdom) 127:8–14. https://doi.org/10.1016/j.polymer.2017.08.049
Wang J, Sun J, Zhou J, Jin K, Fang Q (2017) Fluorinated and thermo-cross-linked polyhedral oligomeric silsesquioxanes: new organic–inorganic hybrid materials for high-performance dielectric application. ACS Appl Mater Interfaces 9:12782–12790. https://doi.org/10.1021/acsami.7b01415
Ghanbari H, Cousins BG, Seifalian AM (2011) A nanocage for nanomedicine: polyhedral oligomeric silsesquioxane (POSS). Macromol Rapid Commun 32:1032–1046. https://doi.org/10.1002/marc.201100126
Jeon JH, Tanaka K, Chujo Y (2013) Rational design of polyhedral oligomeric silsesquioxane fillers for simultaneous improvements of thermomechanical properties and lowering refractive indices of polymer films. J Polym Sci A Polym Chem 51:3583–3589. https://doi.org/10.1002/pola.26757
Tsukada S, Sekiguchi Y, Takai S, Abe Y, Gunji T (2015) Preparation of POSS derivatives by the dehydrogenative condensation of T 8 H with alcohols. J Ceram Soc Jpn 123:739–743. https://doi.org/10.2109/jcersj2.123.739
Huang C, Chang F (2009) Using click chemistry to fabricate ultrathin thermoresponsive microcapsules through direct covalent layer-by-layer assembly. Macromolecules 42:5155–5166. https://doi.org/10.1021/ma900478n
Tokunaga T, Koge S, Mizumo T, Ohshita J, Kaneko Y (2015) Facile preparation of a soluble polymer containing polyhedral oligomeric silsesquioxane units in its main chain. Polym C 6:3039–3045. https://doi.org/10.1039/C5PY00192G
Naka K, Masuoka S, Shinke R, Yamada M (2012) Synthesis of first- and second-generation imidazole- terminated POSS-core dendrimers and their pH responsive and coordination properties. Polym J 44:353–359. https://doi.org/10.1038/pj.2011.145
Yu C-B, Ren L-J, Wang W (2017) Synthesis and self-assembly of a series of n POSS- b -PEO block copolymers with varying shape anisotropy. Molecules 22:622–630. https://doi.org/10.3390/molecules22040622
Zhang W, Fang B, Walther A, Mu AHE (2009) Synthesis via RAFT polymerization of tadpole-shaped organic/inorganic hybrid poly (acrylic acid) containing polyhedral oligomeric silsesquioxane (POSS) and their self-assembly in water. Macromolecules 42:2563–2569
Shockey EG, Bolf AG, Jones PF, Schwab JJ, Chaffee KP, Haddad TS, Lichtenhan JD (1999) Functionalized polyhedral oligosilsesquioxane (POSS) macromers: new graftable POSS hydride, POSS α-olefin, POSS epoxy, and POSS chlorosilane macromers and POSS-siloxane triblocks. Appl Organomet Chem 13:311–327. https://doi.org/10.1002/(SICI)1099-0739
Lichtenhan JD, Otonari YA, Cam MJ, Carr MJ (1995) Linear hybrid polymer building blocks: methacrylate-functionalized polyhedral oligomeric silsesquioxane monomers and polymers. Macromolecules 28:8435–8437. https://doi.org/10.1021/ma00128a067
Hirai T, Leolukman M, Hayakawa T, Kakimoto MA, Gopalan P (2008) Hierarchical nanostructures of organosilicate nanosheets within self-organized block copolymer films. Macromolecules 41:4558–4560. https://doi.org/10.1021/ma800872v
Pramudya I, Rico CG, Lee C, Chung H (2016) POSS-containing bioinspired adhesives with enhanced mechanical and optical properties for biomedical applications. Biomacromolecules 17:3853–3861. https://doi.org/10.1021/acs.biomac.6b00805
Mantz RA, Jones PF, Chaffee KP, Lichtenhan JD, Gilman JW, Ismail IMK, Burmeister MJ (1996) Thermolysis of polyhedral oligomeric silsesquioxane (POSS) macromers and POSS-siloxane copolymers. Chem Mater 8:1250–1259. https://doi.org/10.1021/cm950536x
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
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. Polym (Guildf) 109:254–265. https://doi.org/10.1016/j.polymer.2016.12.049
Sodkhomkhum R, Ervithayasuporn V (2016) Synthesis of poly(siloxane/double-decker silsesquioxane) via dehydrocarbonative condensation reaction and its functionalization. Polymer (United Kingdom) 86:113–119. https://doi.org/10.1016/j.polymer.2016.01.044
Furgal JC, Jung JH, Clark S, Goodson T, Laine RM (2013) Beads on a chain (BoC) phenylsilsesquioxane (SQ) polymers via F− catalyzed rearrangements and ADMET or reverse heck cross- coupling reactions: through chain, extended conjugation in 3-D with potential for dendronization. Macromolecules 46:7591–7604. https://doi.org/10.1021/ma401423f
Jung JH, Furgal JC, Clark S, Schwartz M, Chou K, Laine RM (2013) Beads on a chain (BoC) polymers with model dendronized beads. Copolymerization of [(4-NH2C6H4SiO1.5)6(IPhSiO1.5)2] and [(4-CH3OC6H4SiO1.5)6(IPhSiO1.5)2] with 1,4-Diethynylbenzene (DEB) gives through-chain, extended 3-D conjugation in the excited state tha. Macromolecules 6:7580–7590. https://doi.org/10.1021/ma401422t|
Jung JH, Laine RM (2011) Beads on a chain (BOC) polymers formed from the reaction of [NH 2 PhSiO 1.5 ] x [PhSiO 1.5 ] 10– x and [NH 2 PhSiO 1.5 ] x [PhSiO 1.5 ] 12– x mixtures ( x = 2–4) with the Diglycidyl ether of bisphenol A. Macromolecules 44:7263–7272. https://doi.org/10.1021/ma201032r
Morimoto Y, Watanabe K, Ootake N, Inagaki J, Yoshida K, Ohguma K (2004) POSS patent: US 20040249103
Yoshimatsu M, Komori K, Ohnagamitsu Y, Sueyoshi N, Kawashima N, Chinen S, Murakami Y, Izumi J, Watanabe K, Matuo T, Sakai K, Kunitake M (n.d.) Necklace shaped dimethylsiloxane polymers bearing a polyhedral oligomeric silsesquioxane cage prepared by polycondensation and ring-opening polymerization. pp 2–5
Kunitake M, Sakai K, Hirabayashi C, Morimoto Y, Kunitake M, Sakai K, Hirabayashi C, Morimoto Y (2006) JP 2006022207, n.d
Seino M, Hayakawa T, Ishida Y, Kakimoto MA, Watanabe K, Oikawa H (2006) Hydrosilylation polymerization of double-decker-shaped silsesquioxane having hydrosilane with diynes. Macromolecules 39:3773–3775. https://doi.org/10.1021/ma052631p
Maegawa T, Irie Y, Fueno H, Tanaka K, Naka K (2014) Synthesis and polymerization of a para -disubstituted T8 caged hexaisobutyl-POSS monomer. Chem Lett 43:1532–1534. https://doi.org/10.1246/cl.140515
Maegawa T, Irie Y, Imoto H, Fueno H, Tanaka K, Naka K (2015) Para-bisvinylhexaisobutyl-substituted T 8 caged monomer: synthesis and hydrosilylation polymerization. Polym Chem 6:7500–7504. https://doi.org/10.1039/C5PY01262G
Kunitake M, Nishi T, Yamamoto H, Nasu K, Manabe O, Nakashima N (1994) Preparation and characterization of two-dimensional cross-linked monolayers and Langmuir-Blodgett films of oligo(dimethylsiloxane) copolymer. Langmuir 10:3207–3212. https://doi.org/10.1021/la00021a051
Kato D, Masaike M, Majima T, Hirata Y, Mizutani F, Sakata M, Hirayama C, Kunitake M (2002) Permselective monolayer membrane based on two-dimensional cross-linked polysiloxane LB films for hydrogen peroxide detecting glucose sensors. Chem Commun (Camb):2616–2617. https://doi.org/10.1039/B207957G
Ervithayasuporn V, Sodkhomkhum R, Teerawatananond T, Phurat C, Phinyocheep P, Somsook E, Osotchan T (2013) Unprecedented formation of cis- and trans-di[(3-chloropropyl) isopropoxysilyl]-bridged double-decker octaphenylsilsesquioxanes. Eur J Inorg Chem 2013:3292–3296. https://doi.org/10.1002/ejic.201300283
Acknowledgments
I am deeply grateful to the students who engaged in this research and JNC Corporation and JNC Petrochemical Corporation for continued collaboration. This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “New Polymeric Materials Based on Element-Blocks” (24102006) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2019 Springer Nature Singapore Pte Ltd.
About this chapter
Cite this chapter
Kunitake, M. (2019). Necklace-Shaped Dimethylsiloxane Polymers Bearing Polyhedral Oligomeric Silsesquioxane Cages as a New Type of Organic–Inorganic Hybrid. In: Chujo, Y. (eds) New Polymeric Materials Based on Element-Blocks. Springer, Singapore. https://doi.org/10.1007/978-981-13-2889-3_8
Download citation
DOI: https://doi.org/10.1007/978-981-13-2889-3_8
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-13-2888-6
Online ISBN: 978-981-13-2889-3
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)