Here, we present a multifunctional bio-based polyelectrolyte multilayer-coated hydroxyapatite (HAP@CS@LSF) as a green flame retardant through layer-by-layer inspired assembly using hydroxyapatite, chitosan, and lignosulfonate. The electrostatic interactions deposited the chitosan/lignosulfonate coating on the surface of hydroxyapatite. Subsequently, this multifunctional flame retardant was used to enhance thermal properties, flame retardancy, and mechanical properties of poly(vinyl alcohol). The addition of HAP@CS@LSF to poly(vinyl alcohol) thermally stabilized the poly(vinyl alcohol) composites and resulted in a higher char yield. Furthermore, hydroxyapatite played a critical role and generated synergies with chitosan and lignosulfonate to improve fire safety of poly(vinyl alcohol). Meanwhile, the poly(vinyl alcohol) composites exhibited superior enhancements in tensile strength than that of pure poly(vinyl alcohol).
LiHNingNZhangLet al. Different flame retardancy effects and mechanisms of aluminium phosphinate inPPO, TPU and PP. Polym Degrad Stabil2014; 105:86–95.
2.
NorouziMZareYKianyP. Nanoparticles as effective flame retardants for natural and synthetic textile polymers: application, mechanism, and optimization. Polym Rev2015; 55(3): 531–560.
3.
JiangS-DYaoQ-ZMaY-Fet al. Phosphate-dependent morphological evolution of hydroxyapatite and implication for biomineralisation. Gondwana Res2015; 28(2): 858–868.
4.
LaoutidFBonnaudLAlexandreMet al. New prospects in flame retardant polymer materials: from fundamentals to nanocomposites. Mat Sci Eng R Rep2009; 63(3): 100–125.
5.
ElbasuneySMostafaHE. Synthesis and surface modification of nanophosphorous-based flame retardant agent by continuous flow hydrothermal synthesis. Particuology2015; 22: 82–88.
6.
DongQ-XChenQ-JYangWet al. Thermal properties and flame retardancy of polycarbonate/hydroxyapatite nanocomposite. J Appl Polym Sci2008; 109(1): 659–663.
7.
DongYGuiZJiangSet al. Carbonization of poly(methyl methacrylate) by incorporating hydroxyapatite nanorods during thermal degradation. Ind Eng Chem Res2011; 50(19): 10903–10909.
8.
KöklükayaOCarosioFGrunlanJCet al. Flame-retardant paper from wood fibers functionalized via layer-by-layer assembly. ACS Appl Mater Interfaces2015; 7(42): 23750–23759.
9.
CarosioFAlongiJ. Ultra-fast layer-by-layer approach for depositing flame retardant coatings on flexible PU foams within seconds. ACS Appl Mater Interfaces2016; 8(10): 6315–6319.
10.
CarosioFAlongiJ. Few durable layers suppress cotton combustion due to the joint combination of layer by layer assembly and UV-curing. RSC Adv2015; 5(87): 71482–71490.
11.
CarosioFNegrell-GuiraoCAlongiJet al. All-polymer layer by layer coating as efficient solution to polyurethane foam flame retardancy. Eur Polym J2015; 70: 94–103.
HuangSCenXZhuHet al. Facile preparation of poly(vinyl alcohol) nanocomposites with pristine layered double hydroxides. Mater Chem Phys2011; 130(3): 890–896.
18.
XuLLeiCXuRet al. Hybridization of α-zirconium phosphate with hexachlorocyclotriphosphazene and its application in the flame retardant poly(vinyl alcohol) composites. Polym Degrad Stabil2016; 133: 378–388.
19.
JiangS-DYaoQ-ZZhouG-Tet al. Fabrication of hydroxyapatite hierarchical hollow microspheres and potential application in water treatment. J Phys Chem C2012; 116(7): 4484–4492.
20.
JiangS-DBaiZ-MTangGet al. Fabrication and characterization of graphene oxide-reinforced poly(vinyl alcohol)-based hybrid composites by the sol–gel method. Compos Sci Technol2014; 102: 51–58.
21.
LuLYSunHLPengFBet al. Novel graphite-filled PVA/CS hybrid membrane for pervaporation of benzene/cyclohexane mixtures. J Membrane Sci2006; 281(1–2): 245–252.
22.
ChenYZhangXYuPet al. Stable dispersions of graphene and highly conducting graphene films: a new approach to creating colloids of graphene monolayers. Chem Commun2009; 30: 4527–4529.
23.
ZhangCMYangJQuanZWet al. Hydroxyapatite nano- and microcrystals with multiform morphologies: controllable synthesis and luminescence properties. Cryst Growth Des2009; 9(6): 2725–2733.
24.
LiHFuSPengLet al. Surface modification of cellulose fibers with layer-by-layer self-assembly of lignosulfonate and polyelectrolyte: effects on fibers wetting properties and paper strength. Cellulose2012; 19(2): 533–546.
25.
LawrieGKeenIDrewBet al. Interactions between alginate and chitosan biopolymers characterized using FTIR and XPS. Biomacromolecules2007; 8(8): 2533–2541.
26.
ZhaoC-XLiuYWangD-Yet al. Synergistic effect of ammonium polyphosphate and layered double hydroxide on flame retardant properties of poly(vinyl alcohol). Polym Degrad Stabil2008; 93(7): 1323–1331.
27.
BourbigotSLe BrasMDuquesneSet al. Recent advances for intumescent polymers. Macromol Mater Eng2004; 289(6): 499–511.
28.
ChengKCYuCBGuoWJet al. Thermal properties and flammability of polylactide nanocomposites with aluminum trihydrate and organoclay. Carbohyd Polym2012; 87(2): 1119–1123.
29.
PanYZhanJPanHet al. Effect of fully biobased coatings constructed via layer-by-layer assembly of chitosan and lignosulfonate on the thermal, flame retardant, and mechanical properties of flexible polyurethane foam. ACS Sustainable Chem Eng2016; 4(3): 1431–1438.
30.
FengXWangXXingWet al. Simultaneous reduction and surface functionalization of graphene oxide by chitosan and their synergistic reinforcing effects in PVA films. Ind Eng Chem Res2013; 52(36):12906–12914.
31.
SchartelBPerretBDittrichBet al. Flame retardancyof polymers: the role of specific reactions in the condensed phase. Macromol Mater Eng2016; 301(1):9–35.
32.
LauferGKirklandCMorganABet al. Exceptionally flame retardant sulfur-based multilayer nanocoating for polyurethane prepared from aqueous polyelectrolyte solutions. ACS Macro Lett2013; 2(5): 361–365.
33.
JiangS-DBaiZ-MTangGet al. Synthesis of mesoporous silica@Co–Al layered double hydroxide spheres: layer-by-layer method and their effects on the flame retardancy of epoxy resins. ACS Appl Mater Interfaces2014; 6(16): 14076–14086.
34.
FangMWangKGLuHBet al. Covalent polymer functionalization of graphene nanosheets and mechanical properties of composites. J Mater Chem2009; 19(38): 7098–7105.
35.
LespadePAljishiRDresselhausMS. Model for Raman-scattering from incompletely graphitized carbons. Carbon1982; 20(5): 427–431.
36.
ZengSFuSGuoGet al. Preparation and characterization of nano-hydroxyapatite/poly(vinyl alcohol) composite membranes for guided bone regeneration. J Biomed Nanotechnol2011; 7(4):549–557.
37.
ZhangXFLiuTSreekumarTVet al. Poly(vinyl alcohol)/SWNT composite film. Nano Lett2003; 3(9): 1285–1288.
38.
LayekRKSamantaSNandiAK. The physical properties of sulfonated graphene/poly(vinyl alcohol) composites. Carbon2012; 50(3): 815–827.
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