Synthesis of Furan-based Phosphaphenanthrene Flame Retardant and Its Application in Anti-flammable Epoxy Thermosets

doi:10.7503/cjcu20230494

Abstract

Abstract:

A novel bio-based flame retardant（Furan-2DOPO） was synthesized from 5-hydroxymethylfurfural， furfuramine， phosphorus oxychloride and 9，10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide（DOPO）. Its structure was characterized by Fourier transform infrared spectroscopy， proton- and phosphorus-nuclear magnetic resonance spectroscopy. A series of cured flame retarded epoxy products was obtained by modification of epoxy resin with Furan-2DOPO. The effects of the loading of Furan-2DOPO on the mechanical properties， thermal stability and flame retardant properties of the cured epoxy products were investigated. The results showed that when the addition amount of Furan-2DOPO was only 5%（mass fraction， phosphorus mass fraction was 0.47%）， the oxygen index of the cured epoxy product reached 31.0%， and can pass the UL-94 V-0 test； compared with the unmodified epoxy resin， the peak heat release rate of the cured epoxy products containing 2.5%（mass fraction） and 5%（mass fraction） Furan-2DOPO was decreased by 31% and 35%， respectively. In addition， the tensile strength of the cured epoxy products containing 2.5% and 5% Furan-2DOPO was about 28% higher than that of the unmodified epoxy resin， respectively. The results of char analysis indicated that Furan-2DOPO possessed excellent catalytic charring performance， which was conducive to reducing the escape of combustible gases during combustion， so as to improve the flame retardant performance.

Key words: Epoxy resin, Furan-based phosphaphenanthrene, Flame retardant, Thermal decomposition

CLC Number:

O633

TrendMD:

TANG Gang, TAO Yi, DENG Dan, ZHANG Dongxin, ZHANG Shihua, LIU Xiuyu, WU Qiang, SHEN Haifeng, SUN Junjie. Synthesis of Furan-based Phosphaphenanthrene Flame Retardant and Its Application in Anti-flammable Epoxy Thermosets[J]. Chem. J. Chinese Universities, 2024, 45(4): 20230494.

Figures/Tables 10

References 27

1	Wang X.， Hu Y.， Song L.， Xing W.， Lu H.， Lv P.， Jie G.， Polymer， 2010， 51（11）， 2435—2445
2	Chen Y. J.， Dong L. M.， Ma H. Y.， Qiao Y. F.， Su Y. Y.， Wang C. Z.， Chem. J. Chinese Universities， 2021， 42（3）， 937—945
	陈雅君，董璐铭，马海云，乔亚飞，苏衍跃，王春征. 高等学校化学学报， 2021， 42（3）， 937—945
3	Jiang M. W.， Li S.， Li X. L.， Yin C. H.， Chem. J. Chinese Universities， 2019， 40（12）， 2615—2622
	江民文，李胜，李晓丽，尹晨辉. 高等学校化学学报， 2019， 40（12）， 2615—2622
4	Zang L.， Wagner S.， Ciesielski M.， Müller P.， Döring M.， Polym. Adv. Technol.， 2011， 22（7）， 1182—1191
5	Greiner L.， Döring M.， Eibl S.， Polym. Degrad. Stab.， 2021， 185， 109497
6	Sag J.， Goedderz D.， Kukla P.， Greiner L.， Schönberger F.， Döring M.， Molecules， 2019， 24（20）， 3746
7	Salmeia K. A.， Gaan S.， Polym. Degrad. Stab.， 2015， 113， 119-134
8	Velencoso M. M.， Battig A.， Markwart J. C.， Schartel B.， Wurm F. R.， Angew. Chem. Int. Ed.， 2018， 57（33）， 10450—10467
9	Braun U.， Balabanovich A. I.， Schartel B.， Knoll U.， Artner J.， Ciesielski M.， Doring M.， Perez R.， Sandler J. K. W.， Altstadt V.， Hoffmann T.， Pospiech D.， Polymer， 2006， 47（26）， 8495—8508
10	Lorenzetti A.， Modesti M.， Besco S.， Hrelja D.， Donadi S.， Polym. Degrad. Stab.， 2011， 96（8）， 1455—1461
11	Cao J. F.， Duan H. J.， Zou J. H.， Zhang J. J.， Ma H. R.， Polym. Degrad. Stab.， 2021， 187， 109548
12	Yao Z. Y.， Qian L. J.， Qiu Y.， Chen Y. J.， Xu B.， Li J.， Polym. Adv. Technol.， 2020， 31（3）， 461—471
13	Tang G.， Zhao R. Q.， Deng D.， Yang Y. D.， Chen D. P.， Zhang B.， Liu X. L.， Liu X. Y.， Front. Chem. Sci. Eng.， 2021， 15（5）， 1269—1280
14	Liang H.， Shi W. F.， Poly. Degrad. Stab.， 2004， 84（3）， 525—532
15	Xiao Z. T.， Niu H. X.， Wang W.， Zhou K. S.， Hu Y.， Wang X.， Colloid Surfaces A， 2024， 683， 133008
16	Liang B.， Cao J.， Hong X.， Wang C.， J. Appl. Polym. Sci.， 2013， 128（5）， 2759—2765
17	Khalili P.， Tshai K. Y.， Hui D.， Kong I.， Compos. Part B： Eng.， 2017， 114， 101—110
18	Rajaei M.， Wang D. Y.， Bhattacharyya D.， Compos. Part B： Eng.， 2017， 113， 381—390
19	Tian Y. Z.， Wang Q.， Hu Y. J.， Sun H.， Cui Z. C.， Kou L. L.， Cheng J.， Zhang J. Y.， Polymer， 2019， 178， 121592
20	Li S.， Ren J.， Yuan H.， Yu T.， Yuan W.， Polym. Int.， 2010， 59（2）， 242—248
21	Schartel B.， Bartholmai M.， Knoll U.， Polym. Adv. Technol.， 2006， 17（9-10）， 772—777
22	Wang X.， Kalali E. N.， Wang D. Y.， ACS Sustainable Chem. Eng.， 2015， 3（12）， 3281—3290
23	Dong X.， Yang J.， Hua X.， Nie S.， Kong F.， J. Appl. Polym. Sci.， 2020， 137（3）， 48296
24	Wang X.， Zhou S.， Guo W. W.， Wang P. L.， Xing W.， Song L.， Hu Y.， ACS Sustainable Chem. Eng.， 2017， 5（4）， 3409—3416
25	Niu H.， Nabipour H.， Wang X.， Song L.， Hu Y.， ACS Sustainable Chem. Eng.， 2021， 9（15）， 5268—5277
26	Guo W.， Zhao Y.， Wang X.， Cai W.， Wang J.， Song L.， Hu Y.， Compos. Part B： Eng.， 2020， 192， 107990
27	Guo W.， Wang X.， Huang J.， Zhou Y.， Cai W.， Wang J.， Song L.， Hu Y.， Chem. Eng. J.， 2020， 398， 125661

Sample	m（DGEBA）/g	m（DDM）/g	m（Furan⁃2DOPD）/g	w（Furan⁃2DOPD）（%）	w（P）（%）
EP	81.1	17.9	—	—	—
EP⁃2.5	80.3	17.2	2.5	2.5	0.24
EP⁃5.0	78.4	16.6	5.0	5.0	0.47

Sample	m（DGEBA）/g	m（DDM）/g	m（Furan⁃2DOPD）/g	w（Furan⁃2DOPD）（%）	w（P）（%）
EP	81.1	17.9	—	—	—
EP⁃2.5	80.3	17.2	2.5	2.5	0.24
EP⁃5.0	78.4	16.6	5.0	5.0	0.47

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