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XU Zhiyan, HOU Zeming, YE Xiaolin, et al. Properties and flame retardant mechanism of sulfuretted DOPO derivative in epoxy resin[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 4518-4530. DOI: 10.13801/j.cnki.fhclxb.20211228.001
Citation: XU Zhiyan, HOU Zeming, YE Xiaolin, et al. Properties and flame retardant mechanism of sulfuretted DOPO derivative in epoxy resin[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 4518-4530. DOI: 10.13801/j.cnki.fhclxb.20211228.001
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Properties and flame retardant mechanism of sulfuretted DOPO derivative in epoxy resin

  • School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China

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  • Received Date: October 10, 2021
  • Revised Date: December 01, 2021
  • Accepted Date: December 09, 2021
  • Available Online: December 27, 2021
    Abstract
  • In order to obtain the flame retardant epoxy resin (EP) composites with good comprehensive properties, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide (DOPS) derivative was applied to EP. First, maleic anhydride-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide (MAH-DOPS) was synthesized by the reaction of DOPS and maleic anhydride (MAH). The structure was determined by FTIR, 1H NMR and 31P NMR. Secondly, DOPS and MAH-DOPS were added to EP respectively, to prepare composites DOPS/EP and MAH-DOPS/EP by blending. Thirdly, the thermal stability, flame retardancy and mechanical properties of DOPS/EP and MAH-DOPS/EP were compared. Finally, the effects of MAH-DOPS on the combustion performance and thermal degradation behavior of EP were discussed, and its flame retardant mechanism was analyzed in depth. The results show that the initial decomposition temperature of flame retardant DOPS (205.4℃) is lower than that of MAH-DOPS (235.2℃), and the thermal stability of DOPS/EP is lower than that of MAH-DOPS/EP when the same mass fraction of flame retardants is added, which is consistent with the thermal stability of flame retardants. Both flame retardants DOPS and MAH-DOPS can improve the flame retardancy of EP, and MAH-DOPS/EP has better flame retardant effect. When the amount of flame retardant is 15wt%, limit oxygen index (LOI) values of MAH-DOPS/EP and DOPS/EP are 28.6% and 29.1%, reaching UL-94 V-0 and V-1 rating, respectively. The mechanical test results show that compared with EP, the bending strength of MAH-DOPS/EP increases by 45.8%, while DOPS/EP decreases by 62.5%. The mechanical properties of DOPS/EP system decrease obviously, and almost lose the use value. Cone calorimeter tests show that the average heat release rate (av-HRR) and total heat release (THR) of the composite MAH-DOPS/EP decrease significantly. The results of TG-IR show that the H•, O• or HO• free radicals are captured by the phosphorus-containing free radicals generated by the pyrolysis of MAH-DOPS/EP, and the free radicals are quenched. SEM-EDS results show that MAH-DOPS/EP can form a more complete and compact char layer, and the content of P in the char layer is higher. The study shows that MAH-DOPS plays a flame retardant role in gas phase and condensed phase through flame suppression and char formation respectively, and the gas phase flame retardant mechanism is the main one.
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  • [1]
    GHARIEH A, SEYED M S. A systematic study on the synergistic effects of MWCNTs and core-shell particles on the physicomechanical properties of epoxy resin[J]. Scientific Reports,2021,11:20789.
    [2]
    HUO S Q, SONG P A, YU B, et al. Phosphorus-containing flame retardant epoxy thermosets: Recent advances and future perspectives[J]. Progress in Polymer Science,2021,114:101366. DOI: 10.1016/j.progpolymsci.2021.101366.
    [3]
    YANG S, HUO S Q, WANG J, et al. A highly fire-safe and smoke-suppressive single-component epoxy resin with switchable curing temperature and rapid curing rate[J]. Composites Part B: Engineering,2021,207:108601. DOI: 10.1016/j.compositesb.2020.108601.
    [4]
    DENG J, SHI W F. Synthesis and effect of hyper-branched (3-hydroxyphenyl) phosphate as a curing agent on the thermal and combustion behaviours of novolac epoxy resin[J]. European Polymer Journal,2004,40(6):1137-1143. DOI: 10.1016/j.eurpolymj.2003.12.015.
    [5]
    WANG J Y, QIAN L J, HUANG Z G, et al. Synergistic flame-retardant behavior and mechanisms of aluminum poly-hexamethylene-phosphinate and phosphaphenan-threne in epoxy resin[J]. Polymer Degradation and Stability,2016,130:173-181. DOI: 10.1016/j.polymdegradstab.2016.06.010.
    [6]
    WANG P, CHEN L, XIAO H, et al. Nitrogen/sulfur-containing DOPO based oligomer for highly efficient flame-retardant epoxy resin[J]. Polymer Degradation and Stabi-lity, 2020, 171: 109023.
    [7]
    SHI Y Q, YU B, ZHENG Y Y, et al. Design of reduced graphene oxide decorated with DOPO-phosphanomidate for enhanced fire safety of epoxy resin[J]. Journal of Colloid and Interface Science,2018,521:160-171. DOI: 10.1016/j.jcis.2018.02.054.
    [8]
    ČOLOVIC M, VASILJEVIC J, ŠTIM Z, et al. New sustainable flame retardant DOPO-NH-functionalized polyamide 6 and filament yarn[J]. Chemical Engineering Journal,2021,426(7):130760.
    [9]
    JIANG P, GU X Y, ZHANG S, et al. Synthesis, characterization, and utilization of a novel phosphorus/nitrogen-containing flame retardant[J]. Industrial & Engineering Chemistry Research,2015,54(11):2974-2982.
    [10]
    QIAN L J, QIU Y, SUN N, et al. Pyrolysis route of a novel flame retardant constructed by phosphaphenanthrene and triazine-trione groups and its flame-retardant effect on epoxy resin[J]. Polymer Degradation and Stability,2014,107:98-105. DOI: 10.1016/j.polymdegradstab.2014.05.007.
    [11]
    GU L Q, QIU J H. Effect of DOPO-containing flame retardants on poly(lactic acid): Non-flammability, mechanical properties and thermal behaviors[J]. Chemical Research in Chinese Universitie,2017,33(1):143-149. DOI: 10.1007/s40242-017-6196-9.
    [12]
    YU T, TUERHONGJIANG T, SHENG C, et al. Phosphorus-containing diacid and its application in jute/poly(lactic acid) composites: Mechanical, thermal and flammability properties[J]. Composites Part A: Applied Science and Manufacturing,2017,97:60-66. DOI: 10.1016/j.compositesa.2017.03.004.
    [13]
    YANG S, WANG J, HUO S Q, et al. Preparation and flame retardancy of an intumescent flame-retardant epoxy resin system constructed by multiple flame-retardant compositions containing phosphorus and nitrogen heterocycle[J]. Polymer Degradation and Stability,2015,119:251-259. DOI: 10.1016/j.polymdegradstab.2015.05.019.
    [14]
    LIU Y L. Flame-retardant epoxy resins from novel phosphorus-containing novolac[J]. Polymer,2001,42(8):3445-3454. DOI: 10.1016/S0032-3861(00)00717-5.
    [15]
    WANG X, HU Y, SONG L, et al. Flame retardancy and thermal degradation mechanism of epoxy resin composites based on DOPO substituted organophosphorus oligomer[J]. Polymer,2010,51(11):2435-2445. DOI: 10.1016/j.polymer.2010.03.053.
    [16]
    陈仕梅. 磷杂菲类阻燃剂的合成及在环氧树脂中的应用[D].贵阳: 贵州师范大学, 2018.

    CHEN Shimei. Synthesis of flame retardant based on phospha-phenanthrene and its application in epoxy resin[D]. Guiyang: Guizhou Normal University, 2018(in Chinese).
    [17]
    陈仕梅, 来方, 李霈, 等. 磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究[J]. 高分子学报, 2017(8):1358-1365.

    CHEN Shimei, LAI Fang, LI Pei, et al. Synthesis of flame retardant based on phosphaphenanthrene and flame retardancy study of epoxy resin modified by intumescent flame retardant system composed of ammonium polyphosphate[J]. Acta Polymerica Sinica,2017(8):1358-1365(in Chinese).
    [18]
    罗继永, 张道海, 周密, 等. PBT/TPU/DOPO-MA阻燃复合材料的制备及性能[J]. 化工进展, 2020, 39(8):3221-3229.

    LUO Jiyong, ZHANG Daohai, ZHOU Mi, et al. Preparation and properties of PBT/TPU/DOPO-MA flame retardant composites[J]. Chemical Industry and Engineering Progress,2020,39(8):3221-3229(in Chinese).
    [19]
    LIU P, LIU M M, GAO C, et al. Preparation, characterization and properties of a halogen-free phosphorous flameretarded poly(butylene terephthalate) composite based on a DOPO derivative[J]. Journal of Applied Polymer Science,2013,130(2):1301-1307. DOI: 10.1002/app.39318.
    [20]
    王昱, 罗炎, 张桢. 阻燃型DOPO-马来酸酐改性的环氧树脂研究[J]. 绝缘材料, 2010, 43(3):20-23, 28. DOI: 10.3969/j.issn.1009-9239.2010.03.006.

    WANG Yu, LUO Yan, ZHANG Zhen. Study on epoxy resin modified with flame retardant DOPO-MA[J]. Insulating Materials,2010,43(3):20-23, 28(in Chinese). DOI: 10.3969/j.issn.1009-9239.2010.03.006.
    [21]
    王建航, 许志彦, 张玉鹏, 等. 磷杂菲/环氧树脂复合材料的热分解动力学研究[J]. 功能材料, 2020, 51(11):11152-11158. DOI: 10.3969/j.issn.1001-9731.2020.11.022.

    WANG Jianhang, XU Zhiyan, ZHANG Yupeng, et al. Thermal decomposition kinetics of phosphaphenanthrene/epoxy composites[J]. Journal of Functional Materials,2020,51(11):11152-11158(in Chinese). DOI: 10.3969/j.issn.1001-9731.2020.11.022.
    [22]
    中国国家标准化管理委员会. 塑料用氧指数法测定燃烧行为第1部分: 导则: GB/T 2406.1—2008[S]. 北京: 中国标准出版社, 2008.

    Standardization Administration of the People's Republic of China. Plastics—Determination of burning behaviour by oxygen index—Part 1: Guidance: GB/T 2406.1—2008[S]. Beijing: China Standards Press, 2008(in Chinese).
    [23]
    中国国家标准化管理委员会. 塑料燃烧性能的测定: 水平法和垂直法: GB/T 2408—2008[S]. 北京: 中国标准出版社, 2008.

    Standardization Administration of the People's Republic of China. Plastics—Determination of burning characteristics: Horizontal and vertical test: GB/T 2408—2008[S]. Beijing: China Standards Press, 2008(in Chinese).
    [24]
    International Organization for Standardization. Reaction-to-fire tests—Heat release, smoke production and mass loss rate—Part 1: Heat release rate (cone calorimeter method): ISO 5660-1—2002[S]. Switzerland: International Organization for Standardization, 2002.
    [25]
    中国国家标准化管理委员会. 塑料拉伸性能的测定第2部分: 模塑和挤塑塑料的试验条件: GB/T 1040.2—2006[S]. 北京: 中国标准出版社, 2006.

    Standardization Administration of the People's Republic of China. Plastics—Determination of tensile properties—Part 2: Test conditions for moulding and extrusion plastics: GB/T 1040.2—2006[S]. Beijing: China Standards Press, 2006(in Chinese).
    [26]
    中国国家标准化管理委员会. 塑料弯曲性能的测定: GB/T 9341—2008[S]. 北京: 中国标准出版社, 2008.

    Standardization Administration of the People's Republic of China. Plastics—Determination of flexural properties: GB/T 9341—2008[S]. Beijing: China Standards Press, 2008(in Chinese).
    [27]
    中国国家标准化管理委员会. 塑料悬臂梁冲击强度的测定: GB/T 1843—2008[S]. 北京: 中国标准出版社, 2008.

    Standardization Administration of the People's Republic of China. Plastics—Determination of izod impact strength: GB/T 1843—2008[S]. Beijing: China Standards Press, 2008(in Chinese).
    [28]
    崔锦峰, 王心远, 郭永亮, 等. P元素杂化本征阻燃热塑性聚氨酯弹性体的制备及其性能研究[J]. 功能材料, 2015, 8(46):8050-8054.

    CUI Jinfeng, WANG Xinyuan, GUO Yongliang, et al. Study on preparation and properties of phosphorus hybrid intrinsic flame retardant thermoplastic polyurethane elastomer[J]. Journal of Functional Materials,2015,8(46):8050-8054(in Chinese).
    [29]
    魏振杰, 刘伟区, 李宏静, 等. 含磷有机硅杂化环氧树脂固化体系性能研究[J]. 高分子学报, 2012(2):148-153.

    WEI Zhenjie, LIU Weiqu, LI Hongjing, et al. Propeties of phosphorus-containing organic silicon/epoxy hybrid resin[J]. Acta Polymerica Sinica,2012(2):148-153(in Chinese).
    [30]
    ZHAO Z, JIN Q, ZHANG N, et al. Preparation of a novel polysiloxane and its synergistic effect with ammonium polyphosphate on the flame retardancy of polypropylene[J]. Polymer Degradation and Stability,2018,150:73-85. DOI: 10.1016/j.polymdegradstab.2018.02.007.
    [31]
    LONG L J, CHANG Q F, HE W T, et al. Effects of bridged DOPO derivatives on the thermal stability and flame retardant properties of poly(lactic acid)[J]. Polymer Degradation and Stability,2017,139:55-66. DOI: 10.1016/j.polymdegradstab.2017.03.016.
    [32]
    LIU L, ZHU M H, MA Z W, et al. A reactive copper-organophosphate-MXene heterostructure enabled antibacterial, self-extinguishing and mechanically robust[J]. Chemical Engineering Journal,2022,430(1):132712. DOI: 10.1016/j.cej.2021.132712.
    [33]
    YANG Y Y, LIU J, CAI X F, et al. Antagonistic flame retardancy between hexakis(4-nitrophenoxy) cyclotriphosphazene and potassium diphenylsulf-one sulfonate in the PC system[J]. Journal of Thermal Analysis Calorimetry,2016,126(2):571-583. DOI: 10.1007/s10973-016-5519-2.
    [34]
    BATTIG A, MARKWARTT J, WURM F, et al. Sulfur's role in the flame retardancy of thio-ether-linked hyperbranched poly(phosphoesters) in epoxy resins[J]. European Polymer Journal,2019,122:109390.
    [35]
    张通, 龙丽娟, 何文涛, 等. 9, 10-二氢-9-氧杂-10-磷杂菲-10-氧化物衍生物阻燃聚乳酸的性能研究[J]. 高分子学报, 2019, 50(1): 71-81.

    ZHANG Tong, LONG Lijuan, HE Wentao, et al. Flame-retardant properties of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives in poly(lactic acid)[J]. Acta Polymerica Sinica, 2019, 50(1): 71-81(in Chinese).
    [36]
    徐文静, 龙丽娟, 徐国敏, 等. DOPO衍生物/聚乳酸复合材料的热降解、阻燃及力学性能[J]. 复合材料学报, 2021, 38(9):2848-2861.

    XU Wenjing, LONG Lijuan, XU Guomin, et al. Thermal degradation, flame retardancy and mechanical properties of DOPO derivatives/poly(lactic acid) composites[J]. Acta Materiae Compositae Sinica,2021,38(9):2848-2861(in Chinese).
    [37]
    WANG P, XIA L, JIAN R K, et al. Flame-retarding epoxy resin with an efficient P/N/S-containing flame retardant: Preparation, thermal stability, and flame retardance[J]. Polymer Degradation and Stability,2018,149:69-77. DOI: 10.1016/j.polymdegradstab.2018.01.026.
    [38]
    张通. 桥链基团对双DOPO膦酸酯阻燃聚乳酸性能的影响[D]. 贵阳: 贵州大学, 2019.

    ZHANG Tong. Synthesis of DOPO phosphonates and their flame retardant mechanism on polylactic acid[D]. Guiyang: Guizhou University, 2019(in Chinese).
    [39]
    魏柯. 磷杂菲类阻燃剂的制备及其在聚乳酸中的应用研究[D]. 贵阳: 贵州大学, 2019.

    WEI Ke. Preparation of phosphorus phenanthrene flame retardant and its application in polylactic acid[D]. Guiyang: Guizhou University, 2019(in Chinese).
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