Flame retardants brominated systems,

Kubens (9) found cyanate ester resins were compatible and reactive with epoxy resins. We have confirmed this in our laboratories. Such combinations can be formulated to yield cured materials containing both triazine and oxazoline ring structures. If brominated epoxy resins are employed in such blends, flame retardant materials can be obtained containing as low as 12% bromine versus 20% bromine required to flame retard epoxy systems. Such products show promise for use in printed wiring board laminates. 

Brominated Diphenyl Oxides. Brominated diphenyl oxides are prepared by the bromination of diphenyl oxide. They are often referred to as diphenyl ethers. Taken together, the class constitutes the largest volume of brominated flame retardants. They range ia properties from high melting sohds to hquids. They are used, as additives, ia virtually every polymer system. 

TetrabromobisphenoIA. Tetrabromobisphenol A [79-94-7] (TBBPA) is the largest volume bromiaated flame retardant. TBBPA is prepared by bromination of bisphenol A under a variety of conditions. When the bromination is carried out ia methanol, methyl bromide [74-80-9] is produced as a coproduct (37). If hydrogen peroxide is used to oxidize the hydrogen bromide [10035-10-6] HBr, produced back to bromine, methyl bromide is not coproduced (38). TBBPA is used both as an additive and as a reactive flame retardant. It is used as an additive primarily ia ABS systems, la ABS, TBBPA is probably the largest volume flame retardant used, and because of its relatively low cost is the most cost-effective flame retardant. In ABS it provides high flow and good impact properties. These benefits come at the expense of distortion temperature under load (DTUL) (39). DTUL is a measure of the use temperature of a polymer. TBBPA is more uv stable than decabrom and uv stable ABS resias based oa TBBPA are produced commercially. 

In the 1990s, two types of flame retardants are preferred for outdoor fabrics, ie, a system based on phosphoms and nitrogen such as the precondensate—NH finish and an antimony—bromine system based on decabromodiphenyl oxide [1163-19-5] and antimony(III) oxide (20,40—42). 

Another approach to durable press—flame retardancy uses a combination of a cross-linking system, antimony(III) oxide, and a bromine-containing reactive additive, namely dibromoneopentyl glycol, to achieve dual properties (120,121). 

Acetylene is condensed with carbonyl compounds to give a wide variety of products, some of which are the substrates for the preparation of families of derivatives. The most commercially significant reaction is the condensation of acetylene with formaldehyde. The reaction does not proceed well with base catalysis which works well with other carbonyl compounds and it was discovered by Reppe (33) that acetylene under pressure (304 kPa (3 atm), or above) reacts smoothly with formaldehyde at 100°C in the presence of a copper acetyUde complex catalyst. The reaction can be controlled to give either propargyl alcohol or butynediol (see Acetylene-DERIVED chemicals). 2-Butyne-l,4-diol, its hydroxyethyl ethers, and propargyl alcohol are used as corrosion inhibitors. 2,3-Dibromo-2-butene-l,4-diol is used as a flame retardant in polyurethane and other polymer systems (see Bromine compounds Elame retardants). 

Bromine compounds are often used as flame retardant additives but 15-20ptsphr may be required. This is not only expensive but such large levels lead to a serious loss of toughness. Of the bromine compounds, octabromo-diphenyl ether has been particularly widely used. However, recent concern about the possibility of toxic decomposition products and the difficulty of finding alternative flame retarders for ABS has led to the loss of ABS in some markets where fire retardance is important. Some of this market has been taken up by ABS/PVC and ASA/PVC blends and some by systems based on ABS or ASA (see Section 16.9) with polycarbonates. Better levels of toughness may be achieved by the use of ABS/PVC blends but the presence of the PVC lowers the processing stability. 

Brominated and chlorinated organic flame-retardants can be analysed using either GC-MS or LC-MS. High resolution systems are required to identify the specific isomers. Quantification by bromine or chlorine content is normally achieved using XRF against standards in the same matrix. 

T. Handa, T. Nagashima and N. Ebihara, Synergistic Action of Sb2(>3 with Bromine-Containing Flame Retardants in Polyolefins. II. Structure-Effect Relationships in Flame Retardant Systems," J. of Fire Retardant Chemistry,, 37 (1981). ... 

A Novel System for the Application of Bromine in Flame-Retarding Polymers... 

Experiments pertaining to a new system for the application of bromine to flame retardant polypropylene and foamed polystyrene are described. The FR compound, ammonium bromide, is formed in the amorphous regions of the polymer phase by the interaction of bromine sorbed on the polymer and ammonia, sorbed subsequently. Gaseous nitrogen which is also produced, expands and brings about the rearrangement of the chains to produce a porous structure. The ammonium bromide produced is finely divided and imparts FR properties to the polymer. 

Bromine is applied to flame retarding (FR) polymers in a number of systems, which are divided into two major groups, according to the way in which the FR agent interacts with the polymer [1). In one group, e.g. the reactive systems, the bromine is chemically bound with the polymer. The introduction of the bromine into the polymer molecule can be carried out by copolymerizing a bromine-containing... 

Of the tin additives studied, the anhydrous and hydrated zinc stannates, ZnSnO and ZnSn(OH), respectively, are considerably more effective flame-retardant synergists with the bromine present in the plastic than 8-stannic acid (Figure 1). In line with this observation, oxidic tin-zinc systems have previously been found to exhibit superior flame-retardant properties to tin oxides alone (19-22). In addition, ZnSnO, gives higher values of 01 than Sb20, incorporation levels studied, and, in fact, the 1% ZnSnO - containing plastics outperform samples containing 2% Sb O,. 

We previously reported that brominated aromatic phosphate esters are highly effective flame retardants for polymers containing oxygen such as polycarbonates and polyesters (9). Data were reported for use of this phosphate ester in polycarbonates, polyesters and blends. In some polymer systems, antimony oxide or sodium antimonate could be deleted. This paper is a continuation of that work and expands into polycarbonate alloys with polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and acrylonitrile-butadiene-styrene (ABS). 

The Bromine Industry in particular, points out that non-brominated chemical flame retardants may be very hazardous and that the phase-out of BFRs may not be safe. The non-brominated alternatives listed in the above case studies are likely to be safer if they exhibit less persistence and bioaccumulation in living systems, but some do possess significant toxicity. In the last few years, some agencies have therefore investigated the relative merits of alternatives to BFRs. 

Viberg H, Fredriksson A, Eriksson P. 2002. Neonatal exposure to the brominated flame retardant 2,2, 4,4, 4-pentabromodiphenyl ether causes altered susceptibility if the cholinergic transmitter system in the adult mouse. Toxicol Sci 67 104-107. 

In tile 1990s. two lypes lit flame retardants are preferred lor outdoor fabrics, i.e.. a system based on phosphorus and nitrogen such as the precondensuie-NHi finish and an antimony-bromine system based on decahromodiphetiyl oxide and antimony)III) oxide. 

To improve the fire retardancy of polypropylene, beyond the UL 94 V-2 level, it is necessary to use blends of aromatic bromine fire retardants with antimony trioxide as a synergist. The usual loading is between 35% and 40% fire retardant however, the additional cost may prohibit commercialization. Moreover, the presence of aromatic bromine increases the photooxidation of polypropylene67 69 inactivating hindered amines. To reduce the cost without losing in efficacy the combination of brominated flame-retardant/antimony trioxide system with magnesium hydroxide... 

Back-coating is the major area where bromine-based flame-retardant compounds are used for textiles. This technique is applied primarily in applications such as upholstery and wall coverings. The system would comprise an FR additive with a latex binder, the latter often based on acrylic or ethylene vinylacetate. Use of vinylidene chloride-modified acrylics reduce the amount of tire-retardant additive required. 

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