Self-extinguishing and transparent epoxy resin modified by a phosphine oxide-containing bio-based derivative
Gang Tang1(), Ruiqing Zhao2, Dan Deng3(), Yadong Yang1, Depeng Chen1, Bing Zhang1, Xinliang Liu1, Xiuyu Liu1
1. School of Architecture and Civil Engineering, Anhui University of Technology, Ma’anshan 243002, China 2. College of Resources and Environment, Fujian Agriculture and Forestry University, Fuzhou 350002, China 3. Department of Polymer Science and Engineering, Jiaxing University, Jiaxing 314001, China
A phosphine oxide-containing bio-based curing agent was synthesized by addition reaction between furan derivatives and diphenylphosphine oxide. The molecular structure of the as-prepared bio-based curing agent was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. Dynamic mechanical analysis results indicated that with the increase of bio-based curing agent content, the glass transition temperature of epoxy/bio-based curing agent composites decreased, which was related to the steric effect of diphenylphosphine oxide species that possibly hinder the curing reaction as well as the reduction in the cross-linking density by mono-functional N-H. By the addition of 7.5 wt-% bio-based curing agent, the resulting epoxy composite achieved UL-94 V-0 rating, in addition to limiting oxygen index of 32.0 vol-%. With the increase of content for the bio-based curing agent, the peak of heat release rate and total heat release of the composites gradually decreased. The bio-based curing agent promoted the carbonization of the epoxy matrix, leading to higher char yield with good thermal resistance. The high-quality char layer served as an effective barrier to retard the diffusion of decomposition volatiles and oxygen between molten polymers and the flame. This study provides a renewable strategy for fabricating flame retardant and transparent epoxy thermoset.
W W Guo, S Nie, E N Kalali, X Wang, W Wang, W Cai, L Song, Y Hu. Construction of SiO2@UiO-66 core shell microarchitectures through covalent linkage as flame retardant and smoke suppressant for epoxy resins. Composites. Part B, Engineering, 2019, 176: 107261 https://doi.org/10.1016/j.compositesb.2019.107261
2
W W Guo, X Wang, C S R Gangireddy, J L Wang, Y Pan, W Xing, L Song, Y Hu. Cardanol derived benzoxazine in combination with boron-doped graphene toward simultaneously improved toughening and flame retardant epoxy composites. Composites. Part A, Applied Science and Manufacturing, 2019, 116: 13–23 https://doi.org/10.1016/j.compositesa.2018.10.010
3
X Wang, Y Hu, L Song, W Y Xing, H D Lu, P Lv, G X Jie. Flame retardancy and thermal degradation mechanism of epoxy resin composites based on a DOPO substituted organophosphorus oligomer. Polymer, 2010, 51(11): 2435–2445 https://doi.org/10.1016/j.polymer.2010.03.053
4
Q H Kong, Y L Sun, C J Zhang, H M Guan, J H Zhang, D Y Wang, F Zhang. Ultrathin iron phenyl phosphonate nanosheets with appropriate thermal stability for improving fire safety in epoxy. Composites Science and Technology, 2019, 182: 107748 https://doi.org/10.1016/j.compscitech.2019.107748
5
Q H Kong, T Wu, J H Zhang, D Y Wang. Simultaneously improving flame retardancy and dynamic mechanical properties of epoxy resin nanocomposites through layered copper phenylphosphate. Composites Science and Technology, 2018, 154: 136–144 https://doi.org/10.1016/j.compscitech.2017.10.013
6
S Horold, D E Erftstadt. Flame-retarding thermosetting compositions. US Patent, 6420459 B1, 2002-07-16
7
B Perret, B Schartel, K Stoss, M Ciesielski, J Diederichs, M Doring, J Kramer, V Altstadt. Novel DOPO-based flame retardants in high-performance carbon fibre epoxy composites for aviation. European Polymer Journal, 2011, 47(5): 1081–1089 https://doi.org/10.1016/j.eurpolymj.2011.02.008
8
W Cai, X Feng, B Wang, W Hu, B Yuan, N Hong, Y Hu. A novel strategy to simultaneously electrochemically prepare and functionalize graphene with a multifunctional flame retardant. Chemical Engineering Journal, 2017, 316: 514–524 https://doi.org/10.1016/j.cej.2017.01.017
9
W Cai, J Wang, Y Pan, W Guo, X Mu, X Feng, B Yuan, X Wang, Y Hu. Mussel-inspired functionalization of electrochemically exfoliated graphene: based on self-polymerization of dopamine and its suppression effect on the fire hazards and smoke toxicity of thermoplastic polyurethane. Journal of Hazardous Materials, 2018, 352: 57–69 https://doi.org/10.1016/j.jhazmat.2018.03.021
10
W Cai, T Cai, L He, F Chu, X Mu, L Han, Y Hu, B Wang, W Hu. Natural antioxidant functionalization for fabricating ambient-stable black phosphorus nanosheets toward enhancing flame retardancy and toxic gases suppression of polyurethane. Journal of Hazardous Materials, 2020, 387: 121971 https://doi.org/10.1016/j.jhazmat.2019.121971
11
W Cai, Z Li, X Mu, L He, X Zhou, W Guo, L Song, Y Hu. Barrier function of graphene for suppressing the smoke toxicity of polymer/black phosphorous nanocomposites with mechanism change. Journal of Hazardous Materials, 2021, 404: 124106 https://doi.org/10.1016/j.jhazmat.2020.124106
12
Y Q Shi, C Liu, Z P Duan, B Yu, M H Liu, P A Song. Interface engineering of MXene towards super-tough and strong polymer nanocomposites with high ductility and excellent fire safety. Chemical Engineering Journal, 2020, 399: 125829 https://doi.org/10.1016/j.cej.2020.125829
13
Y Q Shi, B Yu, L J Duan, Z Gui, B B Wang, Y Hu, K K Yuen, Rechard. Graphitic carbon nitride/phosphorus-rich aluminum phosphinates hybrids as smoke suppressants and flame retardants for polystyrene. Journal of Hazardous Materials, 2017, 332: 87–96 https://doi.org/10.1016/j.jhazmat.2017.03.006
14
K Q Zhou, G Tang, R Gao, S D Jiang. In situ growth of 0D silica nanospheres on 2D molybdenum disulfide nanosheets: towards reducing fire hazards of epoxy resin. Journal of Hazardous Materials, 2018, 344: 1078–1089 https://doi.org/10.1016/j.jhazmat.2017.11.059
15
S L Qiu, B Zou, T Zhang, X Y Ren, B Yu, Y F Zhou, Y C Kan, Y Hu. Integrated effect of NH2-functionalized/triazine based covalent organic framework black phosphorus on reducing fire hazards of epoxy nanocomposites. Chemical Engineering Journal, 2020, 401: 126058 https://doi.org/10.1016/j.cej.2020.126058
16
W Z Xu, H Y Yan, G S Wang, Z Q Qin, L J Fan, Y X Yang. A silica-coated metal-organic framework/graphite-carbon nitride hybrid for improved fire safety of epoxy resins. Materials Chemistry and Physics, 2021, 258: 123810 https://doi.org/10.1016/j.matchemphys.2020.123810
17
P M Hergenrother, C M Thompson, J G Smith Jr, J W Connell, J A Hinkley, R E Lyon, R Moulton. Flame retardant aircraft epoxy resins containing phosphorus. Polymer, 2005, 46(14): 5012–5024 https://doi.org/10.1016/j.polymer.2005.04.025
18
L A Mercado, M Galia, J A Reina. Silicon-containing flame retardant epoxy resins: synthesis, characterization and properties. Polymer Degradation & Stability, 2006, 91(11): 2588–2594 https://doi.org/10.1016/j.polymdegradstab.2006.05.007
M Sponton, J C Ronda, M Galia, V Cadiz. Flame retardant epoxy resins based on diglycidyl ether of (2,5-dihydroxyphenyl)diphenyl phosphine oxide. Journal of Polymer Science. Part A, Polymer Chemistry, 2007, 45(11): 2142–2151 https://doi.org/10.1002/pola.21980
22
J Zhao, X Dong, S Huang, X Tian, L Song, Q Yu, Z Wang. Performance comparison of flame retardant epoxy resins modified by DPO-PHE and DOPO-PHE. Polymer Degradation & Stability, 2018, 156: 89–99 https://doi.org/10.1016/j.polymdegradstab.2018.08.007
23
X Tian, Q Yin, Z Wang. Synthesis of diphenylphosphine oxide derivative and its flame retardant application in epoxy resin. Journal of Photopolymer Science and Technology, 2020, 32(6): 769–778 https://doi.org/10.2494/photopolymer.32.769
24
D Q Yang, L M Dong, X D Hou, W K Zheng, J Xiao, J Z Xu, H Y Ma. Synthesis of bio-based poly (cyclotriphosphazene-resveratrol) microspheres acting as both flame retardant and reinforcing agent to epoxy resin. Polymers for Advanced Technologies, 2020, 31(1): 135–145 https://doi.org/10.1002/pat.4755
25
J H Zhang, X Q Mi, S Y Chen, Z J Xu, D H Zhang, M H Miao, J S Wang. A bio-based hyperbranched flame retardant for epoxy resins. Chemical Engineering Journal, 2020, 381: 122719 https://doi.org/10.1016/j.cej.2019.122719
26
C Ma, J Li. Synthesis of an organophosphorus flame retardant derived from daidzein and its application in epoxy resin. Composites. Part B, Engineering, 2019, 178: 107471 https://doi.org/10.1016/j.compositesb.2019.107471
27
W Q Xie, S W Huang, D L Tang, S M Liu, J Q Zhao. Biomass-derived Schiff base compound enabled fire-safe epoxy thermoset with excellent mechanical Properties and high glass transition temperature. Chemical Engineering Journal, 2020, 394: 123667 https://doi.org/10.1016/j.cej.2019.123667
28
J Y Dai, N Teng, J K Liu, J X Feng, J Zhu, X Q Liu. Synthesis of bio-based fire-resistant epoxy without addition of flame retardant elements. Composites. Part B, Engineering, 2019, 179: 107523 https://doi.org/10.1016/j.compositesb.2019.107523
29
Y Z Tian, Q Wang, Y J Hu, H Sun, Z C Cui, L L Kou, J Cheng, J Y Zhang. Preparation and shape memory properties of rigid-flexible integrated epoxy resins via tunable micro-phase separation structures. Polymer, 2019, 178: 121592 https://doi.org/10.1016/j.polymer.2019.121592
30
Z Y Chi, Z W Guo, Z C Xu, M J Zhang, M Li, L Shang, Y H Ao. A DOPO-based phosphorus-nitrogen flame retardant bio-based epoxy resin from diphenolic acid: synthesis, flame-retardant behavior and mechanism. Polymer Degradation & Stability, 2020, 176: 109151 https://doi.org/10.1016/j.polymdegradstab.2020.109151
31
G Tang, X Wang, R Zhang, W Yang, Y Hu, L Song, X L Gong. Facile synthesis of lanthanum hypophosphite and its application in glass-fiber reinforced polyamide 6 as a novel flame retardant. Composites. Part A, Applied Science and Manufacturing, 2013, 54: 1–9 https://doi.org/10.1016/j.compositesa.2013.07.001
32
X Wang, L Song, H Y Yang, W Y Xing, B Kandola, Y Hu. Simultaneous reduction and surface functionalization of graphene oxide with POSS for reducing fire hazards in epoxy composites. Journal of Materials Chemistry, 2012, 22(41): 22037–22043 https://doi.org/10.1039/c2jm35479a
33
G Tang, X L Liu, L Zhou, P Zhang, D Deng, H H Jiang. Steel slag waste combined with melamine pyrophosphate as a flame retardant for rigid polyurethane foams. Advanced Powder Technology, 2020, 31(1): 279–286 https://doi.org/10.1016/j.apt.2019.10.020
34
Y Yan, P Huang, H P Zhang. Preparation and characterization of novel carbon molecular sieve membrane/PSSF composite by pyrolysis method for toluene adsorption. Frontiers of Chemical Science and Engineering, 2020, 13(4): 772–783 https://doi.org/10.1007/s11705-019-1827-y
35
W W Guo, Y Y Zhao, X Wang, W Cai, J L Wang, L Song, Y Hu. Multifunctional epoxy composites with highly flame retardant and effective electromagnetic interference shielding performances. Composites. Part B, Engineering, 2020, 192: 107990 https://doi.org/10.1016/j.compositesb.2020.107990
36
W W Guo, X Wang, J L Huang, Y F Zhou, W Cai, J L Wang, L Song, Y Hu. Construction of durable flame-retardant and robust superhydrophobic coatings on cotton fabrics for water-oil separation application. Chemical Engineering Journal, 2020, 398: 125661 https://doi.org/10.1016/j.cej.2020.125661
37
X Wang, S Zhou, W Y Xing, B Yu, X M Feng, L Song, Y Hu. Self-assembly of Ni-Fe layered double hydroxide/graphene hybrids for reducing fire hazard in epoxy composites. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(13): 4383–4390 https://doi.org/10.1039/c3ta00035d
38
G Tang, L Zhou, P Zhang, Z Q Han, D P Chen, X Y Liu, Z J Zhou. Effect of aluminum diethylphosphinate on flame retardant and thermal properties of rigid polyurethane foam composites. Journal of Thermal Analysis and Calorimetry, 2020, 142(2): 129–137 https://doi.org/10.1007/s10973-019-08897-z
39
Z M Zhu, L X Wang, L P Dong. Influence of a novel P/N-containing oligomer on flame retardancy and thermal degradation of intumescent flame-retardant epoxy resin. Polymer Degradation & Stability, 2019, 162: 129–137 https://doi.org/10.1016/j.polymdegradstab.2019.02.021
