Flame retardants hydroxide

F. Molesky in Recent Advances in Flame Retardamy of Polymeric Materials, Stamford, Coim., 1990 F. Molesky, "The Use of Magnesium Hydroxide for Flame Retarded Low Smoke Polypropylene," Polyolefins IHInternational Conference, Feb. 24,1991, Houston, Tex. 

In order for a soHd to bum it must be volatilized, because combustion is almost exclusively a gas-phase phenomenon. In the case of a polymer, this means that decomposition must occur. The decomposition begins in the soHd phase and may continue in the Hquid (melt) and gas phases. Decomposition produces low molecular weight chemical compounds that eventually enter the gas phase. Heat from combustion causes further decomposition and volatilization and, therefore, further combustion. Thus the burning of a soHd is like a chain reaction. For a compound to function as a flame retardant it must intermpt this cycle in some way. There are several mechanistic descriptions by which flame retardants modify flammabiUty. Each flame retardant actually functions by a combination of mechanisms. For example, metal hydroxides such as Al(OH)2 decompose endothermically (thermal quenching) to give water (inert gas dilution). In addition, in cases where up to 60 wt % of Al(OH)2 may be used, such as in polyolefins, the physical dilution effect cannot be ignored. 

Inert Gas Dilution. Inert gas dilution involves the use of additives that produce large volumes of noncombustible gases when the polymer is decomposed. These gases dilute the oxygen supply to the flame or dilute the fuel concentration below the flammability limit. Metal hydroxides, metal carbonates, and some nitrogen-producing compounds function in this way as flame retardants (see Flame retardants, antimony and other inorganic compounds). 

Thermal Quenching. Endothermic degradation of the flame retardant results in thermal quenching. The polymer surface temperature is lowered and the rate of pyrolysis is decreased. Metal hydroxides and carbonates act in this way. 

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). 

In this case, the components are mixed, the pH adjusted to about 6.0 with sodium hydroxide, and the solution appHed to the textile via a pad-dry-cure treatment. The combination of urea and formaldehyde given off from the THPC further strengthens the polymer and causes a limited amount of cross-linking to the fabric. The Na2HP04 not only acts as a catalyst, but also as an additional buffer for the system. Other weak bases also have been found to be effective. The presence of urea in any flame-retardant finish tends to reduce the amount of formaldehyde released during finishing. 

Ammonia—Gas-Cured Flame Retardants. The first flame-retardant process based on curing with ammonia gas, ie, THPC—amide—NH, consisted of padding cotton with a solution containing THPC, TMM, and urea. The fabric was dried and then cured with either gaseous ammonia or ammonium hydroxide (96). There was Httle or no reaction with cellulose. A very stable polymer was deposited in situ in the cellulose matrix. Because the fire-retardant finish did not actually react with the cellulose matrix, there was generally Httle loss in fabric strength. However, the finish was very effective and quite durable to laundering. 

Uses. The principal use of magnesium hydroxide is in the pulp (qv) and paper (qv) industries (52). The main captive use is in the production of magnesium oxide, chloride, and sulfate. Other uses include ceramics, chemicals, pharmaceuticals, plastics, flame retardants/smoke suppressants, and the expanding environmental markets for wastewater treatment and SO removal from waste gases (87). 

Phosphonium salts are typically stable crystalline soHds that have high water solubiUty. Uses include biocides, flame retardants, the phase-transfer catalysts (98). Although their thermal stabiUty is quite high, tertiary phosphines can be obtained from pyrolysis of quaternary phosphonium haUdes. The hydroxides undergo thermal degradation to phosphine oxides as follows ... 

The aluminum containing compound having the largest worldwide market, estimated to be over 30 x 10 t in 1990, is metal grade alumina. Second, is aluminum hydroxide. In 1990 the market for Al(OH)2 should approach or exceed 3.5 million metric tons which is equivalent to 2.3 million tons on an alumina basis. The spHt between additive and feedstock appHcations for Al(OH)2 (16) is roughly 50 50. Additive appHcations include those as flame retardants (qv) in products such as carpets, and to enhance the properties of paper (qv), plastic, polymer, and mbber products. Significant quantities are also used in pharmaceuticals (qv), cosmetics (qv), adhesives (qv), poHshes (qv), dentifrices (qv), and glass (qv). 

Other flame retardants and/or smoke suppressants can also be used such as magnesium hydroxide, magnesium carbonate, magnesium-zinc complexes and some tin-zinc compositions. Zinc oxide is a common ingredient in many rubber base formulations used as part of the curing system. At the same time, the action of zinc oxide is similar to that of antimony trioxide, but less effective. 

The results obtained by Kuila et al. and Acharya et al. [63,64] from the EVA elastomer blended with lamellar-like Mg-Al layered double hydroxide (LDH) nanoparticles demonstrate that MH nanocrystals possess higher flame-retardant efficiency and mechanical reinforcing effect by comparison with common micrometer grade MH particles. Kar and Bhowmick [65] have developed MgO nanoparticles and have investigated their effect as cure activator for halogenated mbber. The results as shown in Table 4.2 are promising. 

Sodium hydroxide is the alkali usually used in conjunction with dithionite. Sodium carbonate is a possible alternative when Cl Solubilised Sulphur dyes are used but is insufficiently alkaline for the Cl Sulphur brands, requiring careful control if over-reduction and the associated lower yields are to be avoided [30]. Typical concentrations are given in Table 12.24. The system of sodium carbonate and sodium dithionite used to reduce blue and black Cl Solubilised Sulphur dyes is particularly suitable for flame-retardant viscose fibres that are sensitive to strong alkalis, since it preserves a satisfactory level of flame retardancy [30]. It is also possible to use a mixture of dithionite with sodium sulphide in alkaline media. 

The performance of aluminium hydroxide/magnesium hydroxide-filled systems can be enhanced by incorporation of zinc hydroxystannate in halogen-free rubbers giving reduced smoke and toxic gas emission, coupled with higher flame retardancy. This action will be complimentary to the water release and endothermic effects of aluminium hydroxide/magnesium hydroxide filler systems. 

Hitachi Cable Ltd. (35) has claimed that dehydrogenation catalysts, exemplified by chromium oxide—zinc oxide, iron oxide, zinc oxide, and aluminum oxide—manganese oxide inhibit drip and reduce flammability of a polyolefin mainly flame retarded with ATH or magnesium hydroxide. Proprietary grades of ATH and Mg(OH)2 are on the market which contain small amounts of other metal oxides to increase char, possibly by this mechanism. 

Magnesium hydroxide is very basic (high pH) and will degrade PET and PBT if it is used as a flame retardant [39],... 

In 2000, NEC developed an epoxy resin with what it describes as a fire-retardant structure that avoids the need for either TBBA or phosphorus-based flame retardants in circuit boards. The new resin contains a metal hydroxide retardant. The company claims the new board is almost totally free of pollutants, and is easy to process and thermally recycle. By also integrating flame retardant properties within the board, use of the metal hydroxide is minimised, while offering good electrical properties, higher heat resistance and improved processing characteristics. ... 

One of the emerging technologies that is showing great promise is the use of hydrated mineral fillers such as aluminium and magnesium hydroxides, as such materials can provide high levels of flame retardancy without the formation of smoke or corrosive and potentially toxic fumes. The use of fillers as flame retardants has recently been reviewed by Rothon [23]. Essentially the key features are an endothermic decomposition to reduce the temperature, the release of an inert gas to dilute the combustion gases and the formation of an oxide layer to insulate the polymer and to trap and oxidise soot precursors. 

Complex organo-silane products are now emerging which seem able give significant improvements in the impact strength of highly filled polyolefins, especially when used in conjunction with metal hydroxide flame retardants [62]. This may significantly increase their use. 

Aluminium hydroxide has a Moh hardness of about 3 and a specific gravity of 2.4. It decomposes endothermically with the release of water at about 200 °C and this makes it a very useful flame retardant filler, this being the principal reason for its use in polymers. The decomposition temperature is in fact too low for many thermoplastics applications, but it is widely used in low smoke P VC applications and finds some use in polyolefins. For these applications low aspect ratio particles with a size of about 1 micron and a specific surface area of 4-10 m g are preferred. The decomposition pathway can be diverted through the mono-hydrate by the application of pressure, and this may reduce the flame retardant effect [97]. This effect can be observed with the larger sized particles. Although it is chemically the hydroxide, it has for many years been known as alumina trihydrate and by the acronym ATH. 

The production of flame retardant quahty aluminium hydroxide has recently been reviewed [98]. Various crystal forms of aluminium hydroxide exist, but that used for polymer appHcations is Gibbsite. This occurs widely in nature, usually in the rock bauxite, but the natural form is usually not suitable for direct use and synthetic products are nearly always employed. Most aluminium hydroxide is manufactured through the Bayer process used to make alumina for refractory applications. 

The development of the different methods for the production of flame retardant grade magnesium hydroxide has recently been reviewed [100]. Although not a common mineral, there are some workable deposits of brucite, especially in the US and China and product obtained by milling high purity brucite deposits is being marketed, but has so far made little impact. This is probably because the high levels needed for flame retardancy can only be tolerated if the particle size and shape are carefully controlled and this requires the use of synthetic methods of production. 

The traditional flame retardant is based on organobromine compounds together with antimony trioxide as a synergist. Magnesium hydroxide is a good flame retardant due to its high decomposition temperature and smoke suppression properties. It is widely used in thermoplastic materials. However, magnesium hydroxide must be added in portions of some 60% to achieve a reasonable effect. 

S. Chang, T. Xie, and G. Yang, Effects of polystyrene-encapsulated magnesium hydroxide on rheological and flame-retarding properties of HIPS composites, Polym. Degrad. Stab., 91(12) 3266-3273, December 2006. 

Flame retardant - [ALUMENUMCOMPOUNDS - ALUMINUM SULFATE AND ALUMS] (Vol 2) - [AMMONIUMCOMPOUNDS](Vol2) - [VINYL POLYMERS - VINYL CHLORIDE POLYMERS] (Vol24) -ethyleneimines [IMINES, CYCLIC] (Vol 14) -filler for [LEAD COMPOUNDS - LEAD SALTS] (Vol 15) -iron compounds as [IRON COMPOUNDS] (Vol 14) -magnesium hydroxide as filler [MAGNESIUMCOMPOUNDS] (Vol 15)... 

FLAME RETARD ANTS - PHOSPHORUS FLAME RETARDANTS] (Vol 10) Phosphomum hydroxide [4814-27-8]... 

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... 

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