Flame retardants ether

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. 

TetrabromobisphenolA. TBBPA is the largest volume reactive flame retardant. Its primary use is in epoxy resins (see Epoxyresins) where it is reacted with the bis-glycidyl ether of bisphenol A to produce an epoxy resin having 20—25% bromine. This brominated resin is typically sold as a 80% solution in a solvent. TBBPA is also used in the production of epoxy oligomers which are used as additive flame retardants. 

Diester/Ether Diol of Tetrabromophthalic Anhydride. This material [77098-07-8] is prepared from TBPA in a two-step reaction. First TBPA reacts with diethylene glycol to produce an acid ester. The acid ester and propylene oxide then react to give a diester. The final product, a triol having two primary and one secondary hydroxyl group, is used exclusively as a flame retardant for rigid polyurethane foam (53,54). 

TrialkylPhosphates. Triethyl phosphate [78-40-0] C H O P, is a colorless Hquid boiling at 209—218°C containing 17 wt % phosphoms. It may be manufactured from diethyl ether and phosphoms pentoxide via a metaphosphate intermediate (63,64). Triethyl phosphate has been used commercially as an additive for polyester laminates and in ceHulosics. In polyester resins, it functions as a viscosity depressant as weH as a flame retardant. The viscosity depressant effect of triethyl phosphate in polyester resins permits high loadings of alumina trihydrate, a fire-retardant smoke-suppressant filler (65,66). 

Phosphonomethylated Ethers. A phosphoms-containing ether of ceUulose can be prepared by the reaction of cotton ceUulose with chioromethylphosphonic acid [2565-58-4] ia the presence of sodium hydroxide [1310-73-2] by the pad-dry-cure technique (62). Phosphoms contents of between 0.2 and 4.0% are obtained. This finish is durable but has high ion-exchange properties and is flame resistant only as the ammonium salt. DurabUity on medium weight fabrics is obtained with chi oromethylph osph onic diamide. This finish has never penetrated the flame retardant market (63). 

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). 

Alkenylsuccinic anhydrides made from several linear alpha olefins are used in paper sizing, detergents, and other uses. Sulfosuccinic acid esters serve as surface active agents. Alkyd resins (qv) are used as surface coatings. Chlorendric anhydride [115-27-5] is used as a flame resistant component (see Flame retardants). Tetrahydrophthalic acid [88-98-2] and hexahydrophthalic anhydride [85-42-7] have specialty resin appHcations. Gas barrier films made by grafting maleic anhydride to polypropylene [25085-53-4] film are used in food packaging (qv). Poly(maleic anhydride) [24937-72-2] is used as a scale preventer and corrosion inhibitor (see Corrosion and corrosion control). Maleic anhydride forms copolymers with ethylene glycol methyl vinyl ethers which are partially esterified for biomedical and pharmaceutical uses (189) (see Pharmaceuticals). 

Melamine—Formaldehyde Resins. The most versatile textile-finishing resins are the melamine—formaldehyde resins. They provide wash-and-wear properties to ceUulosic fabrics, and enhance the wash durabiHty of flame-retardant finishes. Butylated melamine —formaldehyde resins of the type used in surface coatings may be used in textile printing-ink formulations. A typical textile melamine resin is the dimethyl ether of trimethylolmelamine [1852-22-8] which can be prepared as follows ... 

Propylene oxide has found use in the preparation of polyether polyols from recycled poly(ethylene terephthalate) (264), haUde removal from amine salts via halohydrin formation (265), preparation of flame retardants (266), alkoxylation of amines (267,268), modification of catalysts (269), and preparation of cellulose ethers (270,271). 

A variety of trichloroethylene copolymers have been reported, none with apparent commercial significance. The alternating copolymer with vinyl acetate has been patented as an adhesive (11) and as a flame retardant (12,13). Copolymerization with 1,3-butadiene and its homologues has been reported (14—16). Other comonomers include acrylonitrile (17), isobutyl vinyl ether (18), maleic anhydride (19), and styrene (20). 

When exposed to heat, cotton fabrics, like most substances, increase in temperature to an extent that is proportional to their specific heats. Altering the chemical composition of the fabrics such that large amounts of heat are absorbed and released in repeatable cycles of controllable temperature ranges produces fabrics that are described as temperature adaptable. The process insolubili2es poly(ethylene glycol)s cross-linked with methylolamides in the cotton fabric (78). As with flame-retardant cellulose, attachment is through an ether linkage to the cellulose at a relatively low DS. 

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. 

It should, however, be noted that good flame retardancy is only achieved with the use of flame retardant additives and that some of the best of these, such as the brominated diphenyls and brominated diphenyl ethers, are restricted in their use in some countries. 

Incineration of a collection of polymers with 10 different kinds of brominated flame retardants has been studied under standardized laboratory conditions using varying parameters including temperature and air flow. Polybrominated diphenyl ethers like the deca-, octa-, and pentabromo compounds yield a mixture of brominated dibenzofurans while burning in polymeric matrices. Besides cyclization, debromination/hydrogenation is observed. Influence of matrix effects and burning conditions on product pattern has been studied the relevant mechanisms have been proposed and the toxicological relevance is discussed. 

In 1979, it was stated that poiybrominated aromatic ethers have received little attention (ref. 1). That statement is still applicable. Analyses to characterize this class of commercial flame retardants have been performed using UV (refs. 1-2), GC (refs. 1-6), and GC-MS (refs. 1-4). The bromine content of observed peaks was measured by GC-MS, but no identification could be made. The composition of poiybrominated (PB) diphenyl ether (DPE) was predicted from the expected relationship with polyhalogenated biphenyl, a class which has received extensive attention. NMR (refs. 3-6) was successfully used to identify relatively pure material which had six, or fewer, bromine atoms per molecule. A high performance liquid chromatography (HPLC) method described (ref. 1) was not as successful as GC. A reversed phase (RP) HPLC method was mentioned, but no further work was published. 

Costa, L.G. and Giordano, G. (2007). Developmental neurotoxicity of polybrominated diphenyl ether (PBDE) flame retardants. Neurotoxicology 28, 1047-1067. 

Gustafsson, K., Bjork, M., and Burreau, S. et al. (1999). Bioaccumulation kinetics of bromi-nated flame retardants (polybrominated diphenyl ethers) in blue mussels (Mytilus edu-lis). Environmental Toxicology and Chemistry 18, 1218-1224. 

Hale, R.C., La Guardia, M.J., and Harvey, E.P. et al. (2001). Polybrominated diphenyl ether flame retardants in Virginia freshwater fishes (USA). Environmental Science and Technology 35, 4585 591. 

These industrial chemicals are widely used as the precursors for a wide range of products, which include agrochemicals, pharmaceutical products, polychlorinated biphenyls (PCBs), and polybro-minated diphenyl ether flame retardants. For almost all of them, serious concern has arisen over their adverse environmental effects. 

The structural range of industrially important representatives of these groups is enormous, and includes chlorobenzenes (solvents), polychlorinated biphenyls (PCBs) (hydraulic and insulating fluids), and polybrominated biphenyls and diphenyl ethers (flame retardants). There is widespread concern over both the persistence and the potential toxicity of all these compounds, and sites that have become contaminated during their production represent a threat both to the environment and to human health. Pathways for the aerobic bacterial degradation of chlorobenzenes and chlorobiphe-nyls, and their brominated analogs have been discussed in Chapter 9, Part 1. 

Buser H-R (1986) Polybrominated dibenofurans and dibenzo-p-dioxins thermal reaction products of polybro-minated diphenyl ether flame retardants. Environ Sci Technol 20 404-408. 

The importance of adequate support by database reference material is well illustrated with the following case. After chromatographic separation (TLC, CC), the combination of >H/13C NMR, DI-MS (El), FTIR and HPLC (IJV/VIS, DAD and MS) a flame retardant in a Japanese polypropylene TV cabinet on the European market was identified as tetrabromobisphenol-,S -bis-(2,3-dibromopropyl ether) (TBBP-S) [168]. The result was verified by synthesis of reference material the product was finally identified as Non Nen 52 from Marubishi Oil Chemical Co., Ltd (Osaka), not registered in any spectral database. 

Hydrolysis of polyamide-based formulations with 6 N HC1 followed by TLC allows differentiation between a-aminocaproic acid (ACA) and hexamethylenedi-amine (HMD) (hydrolysis products of PA6 and PA6.6, respectively), even at low levels. The monomer composition (PA6/PA6.6 ratio) can be derived after chromatographic determination of the adipic acid (AA) content. Extraction of the hydrolysate with ether and derivatisa-tion allow the quantitative determination of fatty acids (from lubricants) by means of GC (Figure 3.27). Further HC1/HF treatment of the hydrolysis residue, which is composed of mineral fillers, CB and nonhydrolysable polymers (e.g. impact modifiers) permits determination of total IM and CB contents CB is measured quantitatively by means of TGA [157]. Acid hydrolysis of flame retarded polyamides allows to determine the adipic acid content (indicative of PA6.6) by means of HPLC, HCN content (indicative of melamine cyanurate) and fatty acid (indicative of a stearate) by means of GC [640]. Determination of ethylene oxide-based antistatic agents... 

In order to accomplish with the aforementioned aim, during the first year of project, an extensive research on the different chemical additives used in six industrial sectors was conducted plastics, textiles, electronics, lubricants, leather, and paper. A list of selected chemical additives was identified for each sector and used as a study basis for the rest of the project. This is the case of the decabromo-diphenyl ether (BDE) used in electronics as a flame retardant or the triclosan used in the textile as a biocide. The results of this investigation were presented in the first volume of this book (Global Risk-Based Management of Chemical Additives I Production, Usage and Environmental Occurrence). This volume also included a section of case studies related to the selected additives in different countries (i.e., Denmark, Vietnam, Brazil, India). The main outcomes of the first part of the project are summarized below ... 

Shi T, Chen SJ, Luo XJ, Zhang XL, Tang CM, Luo Y, Ma YJ, Wu JP, Peng XZ, Mai BX (2009) Occurrence of brominated flame retardants other than polybrominated diphenyl ethers in environmental and biota samples from southern China Chemosphere 74(7) 910-916. doi 10.1016/j. chemosphere.2008.10.047... 

Wilford BH, Hamer T, Zhu J, Shoeib M, Jones KC (2004) Passive sampling survey of polybrominated diphenyl ether flame retardants in indoor and outdoor air in Ottawa, Canada ... 

BFRs are one of the last classes of halogenated compounds that are still being produced worldwide and used in high quantities in many applications. In order to meet fire safety regulations, flame retardants (FRs) are applied to combustible materials such as polymers, plastics, wood, paper, and textiles. Approximately 25% of all FRs contain bromine as the active ingredient. More than 80 different aliphatic, cyclo-aliphatic, aromatic, and polymeric compounds are used as BFRs. BFRs, such as polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA), have been used in different consumer products in large quantities, and consequently they were detected in the environment, biota, and even in human samples [26, 27]. 

Modified-polyphenylene oxide (or ether) is a blend of high impact polystyrene (PS) and polyphenylene oxide (PPO), plus thermal stabilizers and a triarylphosphate flame retardant. Studies of the mechanism of the flame retardant in modified-polyphenylene oxide have shown some evidence for both solid phase and vapor phase inhibition (4). Indeed, one is always interested to know whether flame retardant action is on the solid or vapor phase. 

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