Abstract
Organic–inorganic hybrid macrocyclic compounds, polyphenylsilsesquioxanes (cyc-PPSQ), have been synthesized through hydrolysis and condensation reactions of phenyl trichlorosilane. PC/cyc-PPSQ flame retardant materials were obtained by melt blending cyc-PPSQ and PC using a twin-screw extruder. The combustion and thermal decomposition behavior of PC/cyc-PPSQ composites were studied using UL-94, LOI, CONE, TG–FTIR and Py–GC/MS, which showed that the presence of cyc-PPSQ could improve flame retardancy and reduce the heat release and smoke release during combustion of PC. Incorporation of 2 wt% cyc-PPSQ produced a PC/cyc-PPSQ-2 composite which displayed LOI 37.5% and UL-94 V-0 (1.6 mm). The presence of cyc-PPSQ not only improved the flame retardancy of PC, but also did not diminish the glass transition temperature, good mechanical properties and transparency of PC. These results combined with those from TG–FTIR analysis suggest that cyc-PPSQ can promote the initial thermal induced chain-breaking reaction of PC, promote the cross-linking and charring of PC, and facilitate the formation of a dense carbon layer and external SiO2 inorganic barrier layer during combustion. Results from Py–GC/MS indicate that the presence of cyc-PPSQ promotes the generation of phenolic compounds when the composites are pyrolyzed at high temperature.
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References
Mindemark J, Lacey MJ, Bowden T, Brandell D (2018) Beyond PEO—alternative host materials for Li + -conducting solid polymer electrolytes. Prog Polym Sci 81:114–143
Wang Y, Wang B, Wang J, Ren Y, Xuan C, Liu C, Shen C (2018) Superhydrophobic and superoleophilic porous reduced graphene oxide/polycarbonate monoliths for high-efficiency oil/water separation. J Hazard Mater 344:849–856
Zhang X, Fevre M, Jones GO, Waymouth RM (2018) Catalysis as an enabling science for sustainable polymers. Chem Rev 118:839–885
Kausar A (2018) A review of filled and pristine polycarbonate blends and their applications. J Plast Film Sheeting 34:60–97
Chow W, Leung C, Zou G, Dong H, Gao Y (2008) Flame spread over plastic materials in flashover room fires. Constr Build Mater 22:629–634
Daniel Y, Howell B (2018) Phosphorus flame retardants from isosorbide bis-acrylate. Polym Degrad Stab 156:14–21
Wawrzyn E, Schartel B, Karrasch A, Jäger C (2014) Flame-retarded bisphenol A polycarbonate/silicon rubber/bisphenol A bis (diphenyl phosphate): adding inorganic additives. Polym Degrad Stab 106:74–87
Liu C, Yao Q (2017) Design and synthesis of efficient phosphorus flame retardant for polycarbonate. Ind Eng Chem Res 56:8789–8796
Yang Y, Liu J, Cai X (2016) Antagonistic flame retardancy between hexakis (4-nitrophenoxy) cyclotriphosphazene and potassium diphenylsulfone sulfonate in the PC system. J Therm Anal Calorim 126:571–583
Yang S, Lv G, Liu Y, Wang Q (2013) Synergism of polysiloxane and zinc borate flame retardant polycarbonate. Polym Degrad Stab 98:2795–2800
Wawrzyn E, Schartel B, Seefeldt H, Karrasch A, Jäger C (2012) What reacts with what in bisphenol A polycarbonate/silicon rubber/bisphenol A bis (diphenyl phosphate) during pyrolysis and fire behavior? Ind Eng Chem Res 51:1244–1255
Qiu Y, Liu Z, Qian L, Hao J (2017) Gaseous-phase flame retardant behavior of a multi-phosphaphenanthrene compound in a polycarbonate composite. RSC Adv 7:51290–51297
Zhang W, He X, Song T, Jiao Q, Yang R (2014) The influence of the phosphorus-based flame retardant on the flame retardancy of the epoxy resins. Polym Degrad Stab 109:209–217
Annakutty KS, Kishore K (1991) Pyrolysis gas chromatographic studies on polyphosphate esters of bisphenol A. Die Makromolekulare Chemie: Macromol Chem Phys 192:11–20
Despinasse M-C, Schartel B (2012) Influence of the structure of aryl phosphates on the flame retardancy of polycarbonate/acrylonitrile–butadiene–styrene. Polym Degrad Stab 97:2571–2580
Guo J, Wang Y, Feng L, Zhong X, Yang C, Liu S, Cui Y (2013) Performance of a novel sulfonate flame retardant based on adamantane for polycarbonate. Polym Korea 37:437–441
Zhu DY, Guo JW, Xian JX, Fu SQ (2017) Novel sulfonate-containing halogen-free flame-retardants: effect of ternary and quaternary sulfonates centered on adamantane on the properties of polycarbonate composites. RSC Adv 7:39270–39278
Zhang Q, Zhang W, Huang J, Lai Y, Xing T, Chen G, Jin W, Liu H, Sun B (2015) Flame retardance and thermal stability of wool fabric treated by boron containing silica sols. Mater Des 85:796–799
Zhou W, Yang H (2007) Flame retarding mechanism of polycarbonate containing methylphenyl-silicone. Thermochim Acta 452:43–48
Wang J, Xin Z (2010) Flame retardancy, thermal, rheological, and mechanical properties of polycarbonate/polysilsesquioxane system. J Appl Polym Sci 115:330–337
Huang J-C, He C-B, Xiao Y, Mya KY, Dai J, Siow YP (2003) Polyimide/POSS nanocomposites: interfacial interaction, thermal properties and mechanical properties. Polymer 44:4491–4499
Scott DW (1946) Thermal rearrangement of branched-chain methylpolysiloxanes1. J Am Chem Soc 68:356–358
Abe Y, Gunji T (2004) Oligo-and polysiloxanes. Prog Polym Sci 29:149–182
Handke M, Handke B, Kowalewska A, Jastrzębski W (2009) New polysilsesquioxane materials of ladder-like structure. J Mol Struct 924:254–263
Chang S, Matsumoto T, Matsumoto H, Unno M (2010) Synthesis and characterization of heptacyclic laddersiloxanes and ladder polysilsesquioxane. Appl Organomet Chem 24:241–246
Zhang W, Wang X, Wu Y, Qi Z, Yang R (2018) Preparation and characterization of organic-inorganic hybrid macrocyclic compounds: cyclic ladder-like polyphenylsilsesquioxanes. Inorg Chem 57:3883–3892
Gago-Calderón A, Hermoso-Orzáez MJ, Andres-Diaz D, Ramon J, Redrado-Salvatierra G (2018) Evaluation of uniformity and glare improvement with low energy efficiency losses in street lighting LED luminaires using laser-sintered polyamide-based diffuse covers. Energies 11:816
Sánchez-Soto M, Schiraldi DA, Illescas S (2009) Study of the morphology and properties of melt-mixed polycarbonate–POSS nanocomposites. Eur Polym J 45:341–352
Danilaev M, Bogoslov E, Kuklin V, Klabukov M, Khamidullin O, Pol’sky YE, Mikhailov S (2019) Structure and mechanical properties of a dispersedly filled transparent polycarbonate. Mech Compos Mater 55:53–62
Levchik SV, Weil ED (2005) Overview of recent developments in the flame retardancy of polycarbonates. Polym Int 54:981–998
Cheng B, Li X, Hao J, Yang R (2016) The effect of pyrolysis gaseous and condensed char of PC/PPSQ composite on combustion behavior. Polym Degrad Stab 129:47–55
Jang BN, Wilkie CA (2004) A TGA/FTIR and mass spectral study on the thermal degradation of bisphenol A polycarbonate. Polym Degrad Stab 86:419–430
Li X-H, Meng Y-Z, Zhu Q, Tjong S (2003) Thermal decomposition characteristics of poly (propylene carbonate) using TG/IR and Py–GC/MS techniques. Polym Degrad Stab 81:157–165
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This Project was funded by the National Natural Science Foundation of China (21975022) the National Program on Key Research Project (2016YFB0302101), and the International Science and Technology Cooperation Program of China (S2014ZR0465).
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Wu, X., Qin, Z., Zhang, W. et al. Halogen-free and phosphorus-free flame-retarded polycarbonate using cyclic polyphenylsilsesquioxanes. J Mater Sci 55, 10953–10967 (2020). https://doi.org/10.1007/s10853-020-04763-8
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DOI: https://doi.org/10.1007/s10853-020-04763-8