Preparation and flame-retardant mechanism of epoxy foams synergistically modified with DIDOPO and POSS/EG

doi:10.19491/j.issn.1001-9278.2022.09.006

Abstract

Abstract:

For the epoxy foams prepared using a room⁃temperature foaming method with hydrogen as an air source， the carbon layer formed on the surface of the foams is more easily damaged during the combustion process. The damaged carbon layer cannot effectively isolate heat and oxygen， leading to poor fire resistance. Flame⁃retardant In this work， a type of flame⁃retardant epoxy foams was prepared using p⁃phenethyl bridge⁃chain 9，10⁃dihydro⁃9⁃oxa⁃10⁃phosphaphenanthrene⁃10⁃oxide （DIDOPO）， polymethylsilsesquioxane （POSS）， and expandable graphite （EG） as flame retardants. When the mass ratios of DIDOPO to POSS and DIDOPO to EG were set to 3∶1 and 1∶3， respecitively， the epoxy foams obtained an optimal flame⁃retardant effect. With the addition of 20 wt% DIDOPO/POSS composite flame retardants， the epoxy foams achieved a UL 94 V⁃0 classification in the vertical burning test. The addition of 20 wt% DIDOPO/EG composite flame retardants enabled the epoxy foams to obtain a limiting oxygen index of 30.8 vol% together with a UL 94 V⁃0 classification for their flame⁃retardant level. This foaming system also exhibited a certain smoke suppression effect.

Key words: epoxy resin, foam, flame retardant, synergy, flame retardant mechanism

CLC Number:

TQ323.5

YANG Jin, CHEN Pengran, GAO Peixin. Preparation and flame-retardant mechanism of epoxy foams synergistically modified with DIDOPO and POSS/EG[J]. China Plastics, 2022, 36(9): 38-45.

Figures/Tables 12

References 21

1	马玉峰. 轻质阻燃酚醛泡沫材料的制备与构效关系研究［D］.北京：中国林业科学研究院， 2013.
2	王国振. 酚醛树脂泡沫的增韧及阻燃改性研究［D］.昌吉：昌吉学院， 2016.
3	ZHU Z M， XU Y J， LIAO W， et al. Highly flame retardant expanded polystyrene foams from phosphorus⁃nitrogen⁃silicon synergistic adhesives［J］. Industrial & Engineering Chemistry Research， 2017， 56（16）： 4 649⁃4 658.
4	纪文斐. 无卤阻燃聚苯乙烯泡沫的制备和阻燃机理研究［D］. 北京：北京化工大学， 2019.
5	WANG C， WU Y C， LI Y C， et al. Flame⁃retardant rigid polyurethane foam with a phosphorus⁃nitrogen single intumescent flame retardant［J］. Polymers for Advanced Technologies， 2018， 29（1）： 668⁃676.
6	薛竹林，王亚凤，闫莉，等. 反应型含磷多元醇/APP复配阻燃聚氨酯泡沫的制备及性能［J］.塑料科技， 2019， 47（5）： 31⁃36.
	XUE Z L， WANG Y F， YAN L， et al. Preparation and properties of reactive phosphorus containing polyol/app flame retardant polyurethane foam［J］. Plastics Science and Technology， 2019， 47（5）： 31⁃36.
7	姜存华. 阻燃高分子材料的研究进展及其在工程领域的应用［J］.化工设计通讯，2020， 46（8）： 101，109.
	JIANG C H. Research progress of flame retardant polymer materials and its application in engineering［J］. Chemical Engineering Design Communications，2020， 46（8）： 101，109.
8	LIU Q Y， WANG D H， LI Z K， et al. Recent developments in the flame⁃retardant system of epoxy resin［J］. Materials， 2020， 13（9）： 2145.
9	周亚东. 高分子材料阻燃改性研究进展［J］.广州化工，2013， 41（3）： 18⁃20.
	ZHOU Y D. The research progress in flame retardant of polymer materials［J］. Guangzhou Chemical Industry，2013， 41（3）： 18⁃20.
10	DUQUESNE S， LE BRAS M， BOURBIGOT S， et al. Expandable graphite： a fire retardant additive for polyurethane coatings［J］. Fire and Materials， 2003， 27（3）： 103⁃117.
11	LAACHACHI A， BURGER N， APAYDIN K， et al. Is expanded graphite acting as flame retardant in epoxy resin？［J］. Polymer Degradation and Stability， 2015， 117： 22⁃29.
12	WANG Z Y， HAN E， KE W. Influence of expandable graphite on fire resistance and water resistance of flame⁃retardant coatings［J］. Corrosion Science， 2007， 49（5）： 2 237⁃2 253.
13	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.
14	YAN W， YU J， ZHANG M Q， et al. Flame⁃retardant effect of a phenethyl⁃bridged DOPO derivative and layered double hydroxides for epoxy resin［J］. Rsc Advances， 2017， 7（73）： 46 236⁃46 245.
15	YAN W， YU J， ZHANG M Q， et al. Enhanced flame retardancy of epoxy resin containing a phenethyl⁃bridged DOPO derivative/montmorillonite compound［J］. Journal of Fire Sciences， 2018， 36（1）： 47⁃62.
16	WANG X， HU Y A， SONG L， et al. Thermal degradation behaviors of epoxy resin/POSS hybrids and phosphorus⁃silicon synergism of flame retardancy［J］. Journal of Polymer Science Part B⁃Polymer Physics， 2010， 48（6）： 693⁃705.
17	曲立杰. 磷/氮/硅/石墨烯协效阻燃EP的性能研究［D］. 长春：吉林大学， 2020.
18	YAN L， XU Z S， DENG N， et al. Synergistic effects of mono⁃component intumescent flame retardant grafted with carbon black on flame retardancy and smoke suppression properties of epoxy resins［J］. Journal of Thermal Analysis and Calorimetry， 2019， 138（2）： 915⁃927.
19	HUANG J L， GUO W W， WANG X， et al. Combination of cardanol⁃derived flame retardant with SiO₂@MOF particles for simultaneously enhancing the toughness， anti⁃flammability and smoke suppression of epoxy thermosets［J］. Composites Communications， 2021， 27：doi.org/10.1016/j.coco.2021.100904.
20	XIANG Y S， WANG L J， YANG Z， et al. Effect of aluminum phosphinate on the flame⁃retardant properties of epoxy syntactic foams［J］. Journal of Thermal Analysis and Calorimetry， 2019， 137（5）： 1 645⁃1 656.
21	赖学军. 耐水高效膨胀型阻燃剂的制备及其阻燃聚丙烯的研究［D］. 广州：华南理工大学， 2012.

样品名称	TTI/s	T_d/s	PHRR/kW·m^-2	THR·TML/MJ·m^-2·g^-1	CY/%	LOI/%
EP	60	397	991.50	3.04	2.3	21.0
EP 泡沫	13	492	444.36	2.93	3.4	18.4

样品名称	TTI/s	T_d/s	PHRR/kW·m^-2	THR·TML/MJ·m^-2·g^-1	CY/%	LOI/%
EP	60	397	991.50	3.04	2.3	21.0
EP 泡沫	13	492	444.36	2.93	3.4	18.4

样品名称	LOI/%	UL 94
样品名称	LOI/%	t₁/t₂^a	等级
EP/DIDOPO10^b （未发泡）	26.0	6.21/1.20	V⁃0
EP/DIDOPO5	20.0	—^c	NR^d
EP/DIDOPO10	20.6	—	NR
EP/DIDOPO15	22.0	15.33/-	NR
EP/DIDOPO20	22.6	8.31/17.49	V⁃1
EP/DIDOPO25	23.7	4.36/12.28	V⁃1

样品名称	LOI/%	UL 94
样品名称	LOI/%	t₁/t₂^a	等级
EP/DIDOPO10^b （未发泡）	26.0	6.21/1.20	V⁃0
EP/DIDOPO5	20.0	—^c	NR^d
EP/DIDOPO10	20.6	—	NR
EP/DIDOPO15	22.0	15.33/-	NR
EP/DIDOPO20	22.6	8.31/17.49	V⁃1
EP/DIDOPO25	23.7	4.36/12.28	V⁃1

样品名称	LOI/%	UL 94
样品名称	LOI/%	t₁/t₂	等级
EP/DIDOPO16/POSS4	22.6	11.15/2.37	V⁃1
EP/DIDOPO15/POSS5	22.8	7.15/1.37	V⁃0
EP/DIDOPO10/POSS10	22.6	12.78/7.84	V⁃1
EP/DIDOPO5/POSS15	22.8	-	NR
EP/POSS20	20.4	-	NR
EP/DIDOPO11.25/POSS3.75	21.8	17.35/8.76	V⁃1
EP/DIDOPO18.75/POSS6.25	25.0	2.51/0	V⁃0