Synergistic effect of triphenyl phosphate and methyloctabromoether on flame retardancy of polystyrene

doi:10.19491/j.issn.1001-9278.2022.05.007

Abstract

Abstract:

To obtain a high?efficient flame?retardant polystyrene （PS） composite system based on methyloctabromoether （MOBE）， the flame?retardant properties and corresponding mechanisms of the flame?retardant PS compounds with MOBE and triphenyl phosphate （TPP） were investigated using a limiting oxygen index instrument， a cone calorimeter， a thermogravimetric analyzer， and a differential scanning calorimeter. The results indicated that the introduction of TPP and MOBE increased the limited oxygen index （LOI） of PS significantly compared to their use alone. The PS compound containing 3 wt% TPP and 4 wt% MOBE obtained an LOI of 27.7 vol%， which was 26.1 % higher than the compound only containing 4 wt% MOBE. The burning intensity of this PS compound was further depressed， and its effective heat of combustion， peak heat release rate， and total heat release was reduced when compared to those of the compound only containing 4 wt% MOBE. TPP and MOBE could release the flame?retardant elements intensively during the thermal degradation process of PS compounds， exhibiting an efficient gas phase quenching effect. Moreover， the addition of TPP also improved the melt flow rate of PS compounds and reduced their glass transition temperatures. In this case， the generated droplets could take heat away faster from the PS thermal decomposition and finally make TPP and MOBE a better flame?retardant effect.

Key words: flame?retardant polystyrene, triphenyl phosphate, methyloctabromoether, synergistic flame retardancy

CLC Number:

TQ324.24⁺8

YANG Musen, QIAN Lijun, WANG Jingyu, ZHAO Zhen, WANG Guangyu, XIN Xiaohua. Synergistic effect of triphenyl phosphate and methyloctabromoether on flame retardancy of polystyrene[J]. China Plastics, 2022, 36(5): 36-42.

Figures/Tables 13

References 34

1	AHMED L， ZHANG B， SHEN R Q， et al. Fire reaction properties of polystyrene⁃based nanocomposites using nanosilica and nanoclay as additives in cone calorimeter test［J］. Journal of Thermal Analysis and Calorimetry， 2018， 132（3）： 1 853⁃1 865.
2	LIU J C， GUO Y B， ZHANG Y B， et al. Thermal conduction and fire property of glass fiber⁃reinforced high impact polystyrene/magnesium hydroxide/microencapsulated red phosphorus composite［J］. Polymer Degradation and Stability， 2016， 129： 180⁃191.
3	LIU J C， ZHANG Y B， GOU Y B， et al. Effect of carbon black on the thermal degradation and flammability properties of flame⁃retarded high impact polystyrene/magnesium hydroxide/microencapsulated red phosphorus composite［J］. Polymer Composites， 2018， 39（3）： 770⁃782.
4	HAMDANI⁃DEVARENNES S， HAGE REL， DUMAZERT L， et al. Water⁃based flame retardant coating using nano⁃boehmite for expanded polystyrene （EPS） foam［J］. Progress in Organic Coatings， 2016， 99： 32⁃46.
5	VARNAGIRIS S， TUCKUTE S， LELIS M， et al. SiO₂ films as heat resistant layers for protection of expandable polystyrene foam from flame torch⁃induced heat［J］. Journal of Thermoplastic Composite Materials， 2018， 31（5）： 657⁃667.
6	WANG L Y， WANG C， LIU P W， et al. The flame resistance properties of expandable polystyrene foams coated with a cheap and effective barrier layer［J］. Construction and Building Materials， 2018， 176： 403⁃414.
7	WANG Y Q， JIANG H C， NI J Y， et al. Study on the effect of polyFR and its FR system on the flame retardancy and foaming behavior of polystyrene［J］. RSC Advances， 2018， 9（1）： 192⁃205.
8	WU H Z， LIU J H， ZHANG Q， et al. Synergistic flame retardancy of tris（1‐methoxy‐2，2，6，6‐tetramethyl‐piperidin‐4‐yl）phosphite and tris（2，4，6‐tribromophenoxy）‐1，3，5‐triazine/Sb₂O₃ in high‐impact polystyrene［J］. Fire and Materials， 2020， 44（4）： 573⁃584.
9	GELMONT M， YUZEFOVITCH M， YOFFE D， et al. Alkylation of aromatic compounds with pentabromobenzyl bromide and tetrabromoxylene dibromide as a new route to high molecular weight brominated flame retardants［J］. Polymers， 2020， 12（2）： 1⁃18.
10	WANG L C， PAN G W， LYU R L. Study on the char⁃forming and synergistic flame retardant performance of SEBS/HIPS/PPO composites applied for cable［J］. Plastics Rubber and Composites， 2020， 49（5）： 222⁃229.
11	SUN Y， WANG Y Z， QING Y B， et al. A DOPO‐base Schiff derivative used as a flame retardant for polystyrene［J］. Journal of Applied Polymer Science， 2020， 137（40）： 1⁃9.
12	SHI Y Q， XING W Y， WANG B B， et al. Synergistic effect of graphitic carbon nitride and ammonium polyphosphate for enhanced thermal and flame retardant properties of polystyrene［J］. Materials Chemistry and Physics， 2016， 177： 283⁃292.
13	ZHU Z M， RAO W H， KANG A H， et al. Highly effective flame retarded polystyrene by synergistic effects between expandable graphite and aluminum hypophosphite［J］. Polymer Degradation and Stability， 2018， 154： 1⁃9.
14	WU Z G， YANG L Z， ZHAN J， et al. Experimental study on polystyrene with intumescent flame retardants from different scale experiments［J］. Fire and Materials， 2016， 40（1）： 18⁃26.
15	GAO C Q， SHI Y Q， CHEN Y J， et al. Constructing segregated polystyrene composites for excellent fire resistance and electromagnetic wave shielding［J］. Journal of Colloid and Interface Science， 2022， 606： 1 193⁃1 204.
16	LIU J C， ZHANG Y B， GOU Y B， et al. Effect of carbon black on the thermal degradation and flammability properties of flame⁃retarded high impact polystyrene/magnesium hydroxide/microencapsulated red phosphorus composite［J］. Polymer Composites， 2018， 39（3）： 770⁃782.
17	LIU J C， ZHANG Y B， YU Z L， et al. Enhancement of organoclay on thermal and flame retardant properties of polystyrene/magnesium hydroxide composite［J］. Polymer Composites， 2016， 37（3）： 746⁃755.
18	LI M E， YAN Y W， ZHAO H B， et al. A facile and efficient flame⁃retardant and smoke⁃suppressant resin coating for expanded polystyrene foams［J］. Composites Part B： Engineering， 2020， 185： 1⁃7.
19	JI W F， WANG D， GOU J， et al. The preparation of starch derivatives reacted with urea⁃phosphoric acid and effects on fire performance of expandable polystyrene foams ［J］. Carbohydrate Polymers， 2020， 233： 1⁃10.
20	SABA N， PARIDAH M T， JAWAID M， et al. Thermal and flame retardancy behavior of oil palm based epoxy nanocomposites［J］. Journal of Polymers and the Environment， 2018， 26（5）： 1 844⁃1 853.
21	WU H Z， LIU J H， ZHANG Q， et al. Synergistic fire retardancy of bis（1⁃methoxy⁃2，2，6，6⁃tetramethylpiperidin⁃4⁃yl）sebacate and tris（2，4，6⁃tribromophenoxy）⁃1，3，5⁃triazine/Sb₂S₃ in HIPS［J］. Advances in Materials Science and Engineering， 2020： 1⁃16.
22	KAYNAK C， ISITMAN N A. Synergistic fire retardancy of colemanite， a natural hydrated calcium borate， in high⁃impact polystyrene containing brominated epoxy and antimony oxide［J］. Polymer Degradation and Stability， 2011， 96（5）： 798⁃807.
23	BEACH M W， RONDAN N G， FROESE R D， et al. Studies of degradation enhancement of polystyrene by flame retardant additives［J］. Polymer Degradation and Stability， 2008， 93（9）： 1 664⁃1 673.
24	LEVCHIK S V， WEI E D. New developments in flame retardancy of styrene thermoplastics and foams［J］. Polymer International， 2008， 57（3）： 431⁃448.
25	LI H Y， CAI C G， CHEN Y K， et al. Thermal and thermo⁃oxidative degradation of flame retardant high impact polystyrene with triphenyl phosphate and novolac epoxy resin［J］. Journal of Wuhan University of Technology⁃Materials Science Edition， 2007， 22（3）： 486⁃489.
26	ZHANG C W， LI X M， YANG R J， et al. Effects of triphenyl phosphate on styrene suspension polymerization process and flame retardance properties of polystyrene/triphenyl phosphate nanocomposite［J］. Colloid and Polymer Science， 2016， 294： 1 153⁃1 163.
27	NIROUMAND J S， PEIGHAMBARDOUST S J， SHENAVAR A. Polystyrene⁃based composites and nanocomposites with reduced brominated⁃flame retardant［J］. Iranian Polymer Journal， 2016， 25（7）： 607⁃614.
28	ZHANG C W， YANG R J， LI X M， et al. Preparation of polystyrene/triphenyl phosphate composites by suspension polymerization and melt extrusion method⁃A comparative study［J］. Chinese Journal of Polymer Science， 2016，6： 688⁃696.
29	LIN J， LI J， LI X H， et al. Flame retardancy and toughe⁃ning modification of glass fiber⁃reinforced polycarbonate composites［J］. Polymer Journal， 2019， 51（7）： 657⁃665.
30	SHAO L S， XU B， MA W， et al. Flame retardant application of a hypophosphite/cyclotetrasiloxane bigroup compound on polycarbonate［J］. Journal of Applied Polymer Science， 2020， 137： 1⁃13.
31	CHEN Z Q， JIANG M W， CHEN Z W， et al. Preparation and characterization of a microencapsulated flame retardant and its flame⁃retardant mechanism in unsaturated polyester resins［J］. Powder Technology， 2019， 354： 71⁃81.
32	TRUBACHEV S A， KOROBEINICHEV O P， KARPOV A I， et al. The effect of triphenyl phosphate inhibition on flame propagation over cast PMMA slabs［J］. Proceedings of the Combustion Institute， 2020， 38（3）： 4 635⁃4 644.
33	LUO H， ZHOU F， YANG Y Y， et al. Gas⁃condensed phase flame⁃retardant mechanisms of tris（3⁃nitrophenyl） phosphine/triphenyl phosphate/ABS［J］. Journal of Thermal Analysis and Calorimetry， 2017， 132（1）： 263⁃273.
34	NGUYEN T N， TRINH H T， SAM L H， et al. Halogen‐free flame‐retardant flexible polyurethane for textile coating： Preparation and characterisation［J］. Fire and Materials， 2020， 44（2）： 269⁃282.

样品名称	MOBE/g	TPP/g	硬脂酸钙/g	PS/g
PS	0	0	0	100
PS/3 %TPP	0	3	0	97
PS/7 %TPP	0	7	0	93
PS/4 %MOBE	4	0	0.13	95.87
PS/7 %MOBE	7	0	0.13	92.87
PS/3 %TPP/4 %MOBE	4	3	0.13	92.87

样品名称	MOBE/g	TPP/g	硬脂酸钙/g	PS/g
PS	0	0	0	100
PS/3 %TPP	0	3	0	97
PS/7 %TPP	0	7	0	93
PS/4 %MOBE	4	0	0.13	95.87
PS/7 %MOBE	7	0	0.13	92.87
PS/3 %TPP/4 %MOBE	4	3	0.13	92.87

样品	LOI/%	UL 94
样品	LOI/%	t₁/s	t₂/s	是否滴落	阻燃等级
PS	19.2	烧夹	-	是	无级别
PS/3 %TPP	20.2	烧夹	-	是	无级别
PS/7 %TPP	21.1	烧夹	-	是	无级别
PS/4 %MOBE	26.1	0	0	是	V⁃2
PS/7 %MOBE	25.5	0	0	是	V⁃2
PS/3 %TPP/4 %MOBE	27.7	0	0	是	V⁃2

样品	LOI/%	UL 94
样品	LOI/%	t₁/s	t₂/s	是否滴落	阻燃等级
PS	19.2	烧夹	-	是	无级别
PS/3 %TPP	20.2	烧夹	-	是	无级别
PS/7 %TPP	21.1	烧夹	-	是	无级别
PS/4 %MOBE	26.1	0	0	是	V⁃2
PS/7 %MOBE	25.5	0	0	是	V⁃2
PS/3 %TPP/4 %MOBE	27.7	0	0	是	V⁃2

样品	TTI/s	PHRR/kW·m^-2	THR/MJ·m^-2	TSP/m²	av⁃COY/kg·kg^-1	av⁃CO₂Y/kg·kg^-1	av⁃EHC/MJ·kg^-2
PS	35	1 321	134	55.5	0.09	2.48	34.0
PS/4 %MOBE	37	1 006	119	57.9	0.10	2.15	29.8
PS/3 %TPP/4 %MOBE	37	835	105	62.4	0.11	1.89	26.3