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Polymer Degradation and Stability 77 (2002) 325331 www.elsevier.

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Fire retardant mechanism of aliphatic bromine compounds in polystyrene and polypropylene


Jelle Kaspersmaa,*, Cindy Doumena, Sheila Munrob, Anne-Marie Prinsa
a

Great Lakes Technology, Toekomstlaan 13, 2200 Herentals, Belgium b Great Lakes Chemical Corp., Manchester, UK

Received 12 August 2001; received in revised form 8 January 2002; accepted 12 January 2002

Abstract This paper deals with the eective ame retardance of polystyrene and polypropylene with aliphatic bromine compounds. By studying glow wire and UL94 V2 performance of aliphatic hexabromocyclododecane in polystyrene and the mixed aliphatic/aromatic compound tetrabromobisphenol A bis (2,3-dibromopropyl ether) in polypropylene with and without synergists like antimony trioxide and dicumene, it is made plausible that the combination of chain scission and ame poisoning mechanisms causes these compounds to be so eective. The eectiveness of a synergist depends on the use ratio and can be negative depending on the FR test. Also the eect of neutral llers like talc is studied and it is shown that particle size has the strongest eect on the FR test which depends most on polymer ow. The eect of polymer molecular weight is in line with the mechanisms involved. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: FR mechanism; Chain scission; Aliphatic bromine; HBCD; Non Hal; Glow wire test

1. Introduction Brominated ame retardant additives are used for a broad range of applications. Practically all thermoplastics and thermosets can be formulated successfully with various bromine compounds to meet standards like UL94 V0 and V2 for electrical applications and a number of national re standards for building applications. Besides the UL94 standards, which are global, with a preference for V0 in the US and for V2 in Europe, there are also a number of electrical applications in Europe that require a glow wire rating at 750, 850 or 960  C. It is of interest, therefore, to nd out if there is a correlation between V2 and the glow wire ratings. Since for polystyrenes, especially EPS (expanded polystyrene-) and XPS (extruded polystyrene-) foam, HBCD (hexabromocyclododecane) is mainly used as the ame retardant, we selected our commercial product CD-75P for a comparative study of V2 and glow wire in HIPS (high impact polystyrene). Since HIPS for injection moulding applications is subjected to variable resi* Corresponding author. Tel.: +32-1428-6321; fax: +32-14286333. E-mail address: jkaspers@glcc.com (J. Kaspersma).

dence times at elevated temperatures as well as high shear, we used a stabilised version of CD-75P, with 5% of an eective, polymer soluble acid scavenger in order to prevent discoloration. This product is indicated by CD-75Pstab.

Tetrabromo bisphenol A bis(2,3-dibromopropylether) is the most widely used brominated ame retardant for PP (polypropylene) in waste water pipes as well as electrical applications like fuse boxes and kitchen hoods. We used our PE-68 for these evaluations.

0141-3910/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved. PII: S0141-3910(02)00067-8

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1.1. Flame poisoning FR mechanism This mechanism is the FR mechanism according to which halogens interact with the partial oxidation reactions in the gas phase, leading ultimately to complete extinction of the ame, hence ame poisoning [1]. Antimony trioxide is commonly used as synergist for brominated FR additives and is very eective with aromatic products. Antimony trioxide enhances the ame poisoning activity by decomposing the bromine compound and volatilising bromine as SnBr3 and HBr at lower temperature, enabling it to interact in the partial oxidation reactions in the gas phase earlier in the burning process. Although the detailed mechanism of antimony synergism is still under discussion, there is general agreement on the way bromine interacts with the high energy O, H and OH radicals, reducing them to less energetic Br radicals in the presence of a volatile hydrocarbon: Partial OH +CO!CO2+H oxidation: OH +RCH3!RCH2 +H2O RCH2 +O2!RCHO+OH H +O2!OH + O (chain branching) Bromine HBr+OH !H2O+Br interaction: HBr+ O !OH +Br HBr+H $H2+Br HBr+RCH2 $RCH3+Br RBr$R +Br

A question which has puzzled FR specialists for a long time is the relative FR eectiveness of these aliphatic bromine containing products compared to aromatic bromine compounds like DE-83R.

The relative performance of CD-75P and PE-68 vs DE-83R in the UL94-V0 test is shown in Table 1. Apparently the aliphatic and mixed aliphatic/aromatic brominated compounds are much more eective than the fully aromatic reference compound. This is surprising since the V0 rating of a certain compound is often suggested to depend on the bromine/ antimony content only, regardless of molecular structure of the brominated compound. We will try to help understand this phenomenon a little better.

1.2. Chain scission FR mechanism Both polystyrene and polypropylene are polymers with tertiary carbon atoms in the polymer chain, that are susceptible to chain scission by radicals [2]. This eect is used in practice by adding peroxides during

Scheme 1.

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compounding for reducing viscosity of PP, to obtain socalled controlled rheology polypropylene [3]. The same principle is used in polystyrene where peroxides act as synergist for HBCD in FR EPS [4] and dicumene in FR XPS and FR HIPS [5]. These radical generating synergists are active mainly in the melt phase [6]. Dicumene, 2,3-dimethyl-2,3-diphenyl butane has a half-life of 1 h at 210  C [7] and reacts according to the following mechanism in PP. The FR mechanism that causes molecular weig ht reduction and helps cool the ame by enhanced dripping is called the chain scission mechanism (Scheme 1). It is of interest to compare the eects of synergists like antimony trioxide and dicumene with fully aliphatic bromine in CD-75P. This work is aimed at understanding the ame retardance of polystyrene by CD-75P and polypropylene by PE-68, with and without synergists and by linking their eects to ame poisoning and chain scission mechanisms to get a better idea of relative FR eectiveness of aliphatic vs aromatic bromine.

within 10 s after each ignition, with less than 50 s as total burn for 5 samples and no burning drips.

3. Experimental Additives and general-purpose injection moulding resin grades were obtained from the following suppliers: HIPS type 840 from Huntsman, contains 10% rubber PS type 205 from Huntsman, used to dilute rubber content to 6.5%. KM-6100 from Montell for MFI 3. SM-6100 from Montell for MFI 11. WS-6500 S from Montell for MFI 25. Luzenac 1445 from Talc de Luzenac, 10 micron particle size. Prever M10 from Talc de Luzenac, 34 micron particle size. CD-75P, Hexabromocyclododecane from Great Lakes Chemical. PE-68, Tetrabromobisphenol A bis(2,3-dibromopropylether) from Great Lakes Chemical. Timonox Red Star, antimony trioxide from Great Lakes Chemical. Dicumene, 2,3-dimethyl-2,3-diphenyl butane, from Peroxid-Chemie. Compounding was done on a 30 mm co-rotating Werner and Peiderer twin screw extruder with gravimetric feeding stations, using set temperatures between 180 and 190  C for HIPS and between 190 and 210  C for PP. To improve accuracy masterbatches were made rst of the variable components. For injection moulding a BOY 50T machine was used at set temperatures from 180 to 200  C for HIPS and 190 to 210  C for PP. The mould temperature was 40  C for all samples. For glow wire a minimum of 5 samples and for UL94 a minimum of 10 samples were tested to get reliable results. Glow wire plaque thickness was varied from 1 to 3 mm. UL94 bar thickness was varied from 0.8 to 3.2 mm.

2. Glow wire and UL94 test description IEC 606952-10, the glow wire FR test, simulates the eect of thermal stresses which may be produced by heat sources like glowing elements or overloaded resistors, in order to asses the re hazard by a simulation technique. The glow wire test involves intimate contact between a hot wire and the surface of the part to be tested at the point where the moulded part is most vulnerable. The temperature of the wire is maintained at 960, 850, 750, 650 or 550  C. For HIPS usually 960, 850 and sometimes 750  C are used, for PP mainly 960 or 850  C. A contact time of 30 s between the hot wire and the part surface is maintained and, in order to pass, the test part should not maintain a ame for more than 30 s after retraction of the wire and should not generate burning drips. The ocial standard requires testing to be done on the moulded part but, for the purpose of this study, test plaques with varying thickness were used. The UL94 standard evaluates the actual response to heat and ame of materials under controlled laboratory conditions. The UL94 test is performed with a 20 mm vertical ame by twice contacting a moulded sample with dimensions of 12712.7thickness in mm for 10 s. In order to pass UL94 V2, the ame should extinguish within 30 s after each ignition and with a maximum burn time of 250 s for 5 samples. Burning drips are allowed. For UL94 V0 the ame should extinguish

4. Results and discussion 4.1. HIPS The behaviour of HIPS with CD-75Pstab in glow wire and UL94 V2 tests has been described in detail in a previous paper [8]. An overview of the results is given in Table 2 for the eects on glow wire rating and in Table 3 for UL94 V2 in HIPS. Since HIPS is usually made in bulk with a xed polymer composition, as far as PS (polystyrene) molecular weight and grafted polybutadiene rubber content is concerned, ow is varied by adjusting the content of mineral oil ow modier and impact resis-

Table 1 FR Load levels for 1.6 mm UL94-V0 HIPS PP 8% CD-75P+ 3% Sb2O3=6% Br 10% PE 68+3% Sb2O3=7% Br 11.5% DE-83R+3.5% Sb2O3=9.5% Br 23% DE 83R+10% Sb2O3=19% Br

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tance by dilution of the rubber through blending with crystal PS or by adding more rubber. The surprising maximum requirement of FR at 1.5 mm thickness is caused by the strong eect of moulding stress. Moulding stress is highest in the thinnest plaques. At a thickness well over 1.5 mm, the increased mass causes the plaque to burn less readily, resulting in a reduced FR requirement. The most critical thickness, as prescribed by the glow wire test is thus 1.5 mm, in line with commercial experience. Moulding stress is shown to be a major factor in determining the FR requirement for glow wire. We optimised moulding conditions and found that high injection speed and short holding pressure time yield minimal stress levels especially on the thinner gages of

1.5 mm or less. High moulding stress was obtained by using low injection speed and long holding pressure time. Conditions for minimal stress were used as a standard. In HIPS glow wire performance is usually measured at 960  C. Table 2 shows that the minimum FR load level required is about the same at 960 or 850  C, but substantially lower at 750  C. At 650 or 550  C hardly any FR is needed to pass the test. Mineral oil does not seem to be a dominant factor. Only at addition levels well over 3% will some more FR additive be needed. The negative eect of the more combustible mineral oil apparently dominates its positive eect on ow. When comparing performance of PE-68, a mixed aliphatic/aromatic bromine compound, we applied 2%

Table 2 Glow wire 960  C performance of CD-75Pstab in HIPS with 6.5% rubber Variable Plaque thickness t Value 1.0 mm 1.5 mm 3.0 mm High Low 750  C 850  C 960  C 1.8% MFI 7 0.9% MFI 3 5.9% PE-68 5% soluble 5% insoluble 25% insoluble 6.5% 9.5% 0.4% 4.0% 1.2% 1.7% CD-75stab loading 2.1% 4.2% 2.1% 3.0% 4.2% 0.85% 4.2% 4.2% 4.2% 4.2% 4.2% 4% CD-75P 4% CD-75P 4% CD-75P 4.2% 6.0% 4.2% 4.0% 0% 4.2% 3.5% 5.0% Result Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass Fail Pass Fail/pass Fail/pass Pass Pass Pass Pass Fail Pass Pass Pass Average burn time (s) 1020 1020 1020 1020 1020 05 05 1020 39 5 1020 > 60 1020 > 60 1/5 Flaming drips 1/5 1020 1020 16 5 > 60 s, Flaming drips 16 12 14

Molding stress, t=1.5 mm Glow wire test temperature, t=1.5 mm

Mineral oil, t=1.5 mm Aliphatic vs Mixed Br, PE-68 Eect of acid scavenger, t=1.5 mm

Rubber, t=1.5 mm Dicumene, t=1.5 mm

Sb2O3, t=1.5 mm

Table 3 UL94 V2 performance of CD-75Pstab in HIPS with 6.5% rubber Variable UL bar thickness t Value 3.2 mm 1.6 mm 0.8 mm 0.16% 1.6% 1.6% 0.53% 1.6% 2.0% CD-75Pstab loading (%) 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 0.7 Result Pass Pass Pass Pass Pass Pass Fail Pass Fail Fail Fail Average burn time (s) 8.0 5.2 1.1 5.2 1.1 1.0 > 30 5.2 > 30 > 30 > 30

Dicumene, t=1.6 mm

Sb2O3, t=1.6 mm

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aliphatic+2% aromatic bromine in PE-68 vs 3% aliphatic bromine in CD-75Pstab. The negative performance of PE-68 indicates that at least 3% aliphatic Br is needed. The extra amount of aromatic Br does not help without Sb2O3. The comparison of acid scavenging stabilisers showed that a fully polymer-soluble acid scavenger gives the best results at 5% addition. Another non-soluble scavenger at 5% addition gave one failure out of ve because of a long burn time. The addition of 25% of another, less eective acid scavenger caused failure by aming drips in one sample out of ve. Apparently the addition of a ne ller-type scavenger causes the material to ow away from the hot wire less eectively. Rubber content is a major factor for FR addition rate, possibly because of the oxidation sensitivity of partly unsaturated butadiene rubber. Higher rubber contents may also have a negative eect on retraction of the material away from the hot wire and hence increase the burn time. FR requirement increases almost linearly with rubber content. Dicumene, a synergistic radical generator, has a positive eect on burn time but cannot pass the glow wire test without bromine. Apparently a certain contribution of ame poisoning by HBr in the gas phase is still needed, even though chain scission occurs more rapidly, as shown by the speed of dripping. In the presence of CDTable 4 UL94 V2 performance of PE-68 in PP Variable Sb2O3 loading

75Pstab aming drips disappear in the glow wire test and the burn time is reduced. Antimony trioxide, the standard synergist with aromatic bromine for ame poisoning, shows a neutral eect on glow wire performance. Without CD-75Pstab it is inactive. With CD-75Pstab it has little eect on burn time. It looks like the glow wire test needs ame poisoning activity and does benet somewhat from the extra activity oered by Sb2O3, as shown by the reduced CD-75Pstab loading of 3.5%. Table 3 shows that UL V2 is a less demanding FR test in HIPS than is the glow wire test. Also, the eect of bar thickness is relatively small. Thicker gauges need more FR additive, since it takes more time to preheat a thick bar and make it drip than a thin one. The eect of Dicumene is positive as shown by the reduction of the burn time, but, as in the glow wire test, Dicumene needs some bromine to qualify for V2. Some ame poisoning activity is still needed, even though burning drips are allowed. The eect of antimony is strongly negative. Volatilising Br as SbBr3 has a strong negative eect on the chain scission activity. UL V2 seems to depend more on chain scission than the glow wire test. Apparently in the V2 test, enhanced ame poisoning does not balance the loss of chain scission, unlike in the glow wire test shown above.

PE-68 loading (%)

Result/gage (mm) 3 1.6 Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass 0.8 Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass

PE-68/Sb2O3 ratio

MFI, PE-68/Sb2O3=3:1 Talc ller, PE-68/Sb2O3=3:1 Copolymer, PE-68/Sb2O3=3:1

0.25% 0.5% 0.75% 1.5% 3 11 25 20% 34 mm 20% 10 mm Homopolymer 10% ethylene

1.5 1.5 1.5 1.5 2.0 1.5 1.5 1.5 1.5 1.5 1.5

Fail 3/10 Pass Fail 1/10 Fail 4/10 Pass Pass Pass Pass Pass Pass Pass

Table 5 Glow wire performance of PE-68/Sb2O3 in PP Variable Glow wire temperature, T Value 960  C 960  C 960  C 850  C 850  C 850  C 20% 34 mm 20% 10 mm PP Homopol 10% Ethylene PE-68+Sb2O3 loading 0.5+0.17% 1.0+0.33% 1.5+0.5% 0.5+0.17% 1.0+0.33% 1.5+0.5% 2.0+0.67% 1.0+0.33% 1.0+0.33% 1.0+0.33% Result Fail Pass Pass Fail Pass Pass Fail Pass Pass Pass 3 > 60 35 30 > 60 10 8 > 60 1040 1040 1040 1.5 > 60 25 24 > 60 5 4 > 60 sec 530 sec 530 sec 530 sec 1.0 mm > 60 sec 21 sec 10 sec > 60 sec 3 sec 2 sec

Talc ller, T=850, 960  C Copol, T=850, 960  C

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4.2. PP The full results of PE-68 for V2 and glow wire in PP have been reported elsewhere [9]. In polypropylene we have used Sb2O3 as a variable synergist only, but Dicumene and its oligomers are patented with aliphatic brominated ame retardants in polypropylene since 1970 [10]. The summarised results are shown in Table 4 for UL94 V2 and in Table 5 for the glow wire test. Table 4 shows an optimum in V2 performance for a Sb2O3/PE-68 weight ratio around 0.33 (Sb/Br atom ratio 0.27). Little change in burn time was found between 0.33 and 0.25 weight ratio (Sb/Br atom ratio 0.270.20). Under the assumption that chain scission is linked to aliphatic and ame poisoning to aromatic bromine, the theoretical optimum atom ratio would amount to 0.17: too little antimony causes insucient ame poisoning activity and too much antimony volatilises aliphatic bromine, reducing chain scission activity. since a weight ratio for Sb2O3/PE-68 of 0.33 is most often used in practice, we also kept it constant at this value for this evaluation. A similar optimum ratio for Sb/Br was found by Handa et al. [11] for 2,3-dibromopropyl pentabromophenyl ether. For LOI they found experimentally an optimum of 0.22, for heat release an optimal ratio of 0.25 and for maximum SbBr3 volatilisation a ratio between 0.20 and 0.28. With the chain scission/ame poisoning model for this aliphatic/aromatic bromine compound, they could have calculated an optimal Sb/Br atom ratio of 0.24. A perfect t for this model that assumes the need for Sb2O3 synergist for aromatic bromine for ame poisoning only, while aliphatic bromine should stay in the melt for chain scission, requiring no Sb2O3 at all.

Copolymer ethylene content below 10% does not have an eect on UL94 V2 loading of PE-68/antimony. Possibly because at this low level of ethylene the reduction of the tertiary carbon concentration is too low to be noticed. Also in polyethylene tertiary carbon plays a role in the UL V2 mechanism, made plausible by the fact that in LDPE with more branching less PE-68 is needed for V2 than in HDPE. The large dierence in bromine requirement between PE-68 and DE-83R for UL94 V0 in polypropylene indicated in Table 1, is probably also caused by the Chain Scission mechanism. By means of this mechanism the UL bar is additionally cooled by (non-burning) fast dripping, such that substantially less Br is needed for Flame Poisoning than with DE-83R, which contains only aromatic bromine and does not benet from this favourable contribution. Compared to HIPS there is a very weak eect of plaque thickness for glow wire in polypropylene: 3 mm plaques have only somewhat longer burn times. The eect of moulding stress is not present in crystalline polymers like polypropylene to the extent it is in amorphous HIPS. The glow wire test is a less demanding test in PP than UL94 V2. This may be related to enhanced chain scission in PP vs PS, because of fewer stable tertiary C-atoms in PP. It is also possible that this dierence is caused by the presence of aromatic Br and Sb2O3 and consequently more ame poisoning activity in PP, which is more favourable in the glow wire test. Talc of 10 mm particle size does not eect glow wire behaviour of PP, even at 20% loading. But the smaller 34 mm particles do eect the way the material retracts from the hot wire rather strongly. Even at the double FR loading it still does not pass. This is surprising since in UL94 V2, where dripping is most important, no such eect is noticed. The absence of an eect of 10% ethylene in the copolymer on glow wire rating means that also here the dilution of tertiary C-atoms has no measurable eect. 4.3. Non-halogen FR compound for PP The FR mechanism where halogen is not required is the charring mechanism. This is a suitable mechanism for naturally charring polymers, but requires the addition of a char source as well as a charring additive for products like PP or PS. Such FR systems are often based on pentaerithritol as the char source and a phosphorous compound as the charring additive. These products can be quite eective for UL94 V0, but have the disadvantage of a limited eectiveness for V2 and Glow Wire. As shown in Table 6, there is relatively little dierence between FR loading required for V0 and V2 for Non Halogen ame retardants. The product NH1511 is an optimised version of NH-1197, including some proprietary charring synergists.

The eect of reduced molecular weight is as may be expected for a chain scission mechanism: for higher MFI (melt ow index) less FR is needed. At MFI 25 no further reduction is found: in the UL test dripping is so fast, that a continuous ow of burning drips keeps the test bar hot, thus defeating the cooling eect of fast dripping. An eect of 20% ller loading is not seen. Both 34 and 10 m particle size fail to interfere noticeably with the dripping mechanism for V2.

J. Kaspersma et al. / Polymer Degradation and Stability 77 (2002) 325331 Table 6 Relative load levels for V0 and V2 in PP for bromine vs. non-hal FR FR additive PE-68+Sb2O3 NH-1511 UL94 V2 1.5+0.3% 23% UL94 V0 10+3.3% 28% Ratio V0/V2 6.6 1.2

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polyprolylene. Also the ecient behaviour of these compounds for UL94 V0 is explained by a combined mechanism, but only for polymers with tertiary carbon atoms in the polymer backbone like polystyrene or polypropylene. By comparison, charring FR additives are much less eective for FR standards like UL94 V2 and glow wire. Further work should be invested in studying the relative eectiveness of PE-68 vs CD-75P in pure polystyrene, without rubber impact modier and CD-75P vs PE-68 in polypropylene homopolymer. Only then can we separate the relative eectiveness of aliphatic vs mixed aliphatic-aromatic bromine compounds from the natural tendency for chain scission of polystyrene vs polypropylene.

References Where both V2 and glow wire benet from the additive eect of chain scission and ame poisoning when aliphatic bromine is involved, the charring mechanism does not allow a low addition level to enhance chain scission. The charring mechanism is incompatible with chain scission, since it forces the polymer to develop a sti continuous surface for protection, rather than to break up and ow away as in chain scission. Sometimes no V2 rating is found at all: when reducing the FR loading from a V0 level, the rating passes directly to an unclassied one, not via V2.
[1] International ammability handbook, 2nd ed. Ju rgen Troitsch, 1990. p. 46. [2] Larsen ER. Halogenated ame retardants. In: Kirk Othmer encyclopedia of chemical technology, vol. 10. John Wiley, 1980. p. 382. [3] Kowalski R. Reactive extrusion. Hanser: Ronald Kowalski, 1992. p. 8. [4] ARCO US Patent 1990, No. 4980382. [5] BASF German Patent 1968, No. 1272533. [6] Gouinlock EV, Porter JF, Hindersinn RR. J Fire Flammability 1971;2:206. [7] Half life time of 1 h at 210  C for a 0.1 m solution in benzene. Peroxid-Chemie Data Sheet for CCDFB-90. [8] Doumen C, Prins A-M, Kaspersma J. Flame retardance of polystyrene. 5th ed. Addcon World, 1999. [9] Prins A-M, Doumen C, Kaspersma J. Glow wire and V-2 performance of brominated FRs in PP, Flame Retardants. London, 2000. [10] BASF German Patent 19702048310 720406; Vamp Srl Italian Patent 198025311 19801014; Tosoh Corp Japanese Patent 1992 337112 199221217. [11] Handa T, Nagashima T, Ebihara N. Fire and Materials 1979; 3(2):61.

5. Conclusions The various eects on glow wire and UL94 V2 studied here, make it plausible that a combination of chain scission and ame poisoning mechanism is responsible for the very eective aliphatic and mixed aliphatic/aromatic brominated FR additives in polystyrene and