Retarding additives

There have been reviews of flammabihty (63—67), methods that can be used to enhance the flame resistance of acryhc and modacryhc fibers (68), and the mechanism of fiame-retardant additives (69). 

The materials of attention in promoting fire safety are generally organic polymers, both natural, such as wood (qv) and wool (qv), and synthetic, nylon (see Polyamides), vinyl, and mbber (qv). Less fire-prone products generally have either inherently more stable polymeric stmctures or fire-retardant additives. 

Useful materials incorporating fire-retardant additives are not always straightforward to produce. Loadings of 10% are common, and far higher levels of flame retardants are used in some formulations. These concentrations can have a negative effect on the properties and functions for which the materials were originally intended. Product-specific trade-offs are generally necessary between functionaUty, processibiUty, fire resistance, and cost. 

Flame-retardant additives are capable of significant reduction in the ha2ard from unwanted fires, and techniques are now available to quantify these improvements. Combined with an understanding of fire-retardant mechanisms, polymer-retardant interactions, and reuse technology, formulations optimi2ed for pubHc benefit and manufacturing practicaUty can be selected. 

Addition of approximately 40% of the halogen flame retardants are needed to obtain a reasonable degree of flame retardancy. This usually adversely affects the properties of the plastic. The efficiency of the halogens is enhanced by the addition of inorganic flame retardants, resulting ia the overall reduction of flame-retardant additive package and minimising the adverse effects of the retardants. 

Molybdenum Oxide. Molybdenum compounds incorporated into flexible PVC not only increase flame resistance, but also decrease smoke evolution. In Table 10 the effect of molybdenum oxide on the oxygen index of a flexible PVC containing 50 parts of a plasticizer is compared with antimony oxide. Antimony oxide is the superior synergist for flame retardancy but has Httle or no effect on smoke evolution. However, combinations of molybdenum oxide and antimony oxide may be used to reduce the total inorganic flame-retardant additive package, and obtain improved flame resistance and reduced smoke. 

Brominated Additive Flame Retardants. Additive flame retardants are those that do not react in the appHcation designated. There are a few compounds that can be used as an additive in one appHcation and as a reactive in another. Tetrabromobisphenol A [79-94-7] (TBBPA) is the most notable example. Tables 5 and 6 Hst the properties of most commercially available bromine-containing additive flame retardants. 

Red Phosphorus. This aHotropic form of phosphoms is relatively nontoxic and, unlike white phosphoms, is not spontaneously flammable. Red phosphoms is, however, easily ignited. It is a polymeric form of phosphoms having thermal stabiUty up to ca 450°C. In finely divided form it has been found to be a powerful flame-retardant additive (26,45—47). In Europe, it has found commercial use ia molded nylon electrical parts ia a coated and stabilized form. Handling hazards and color have deterred broad usage. The development of a series of masterbatches by Albright Wilson should facihtate further use. 

A series of compounded flame retardants, based on finely divided insoluble ammonium polyphosphate together with char-forming nitrogenous resins, has been developed for thermoplastics (52—58). These compounds are particularly useful as iatumescent flame-retardant additives for polyolefins, ethylene—vinyl acetate, and urethane elastomers (qv). The char-forming resin can be, for example, an ethyleneurea—formaldehyde condensation polymer, a hydroxyethylisocyanurate, or a piperazine—triazine resin. 

Blends of triaryl phosphates and pentabromodiphenyl oxide are leading flame-retardant additives for flexible urethane foams. A principal advantage is their freedom from scorch. 

Triphenyl phosphate [115-86-6] C gH O P, is a colorless soHd, mp 48—49°C, usually produced in the form of flakes or shipped in heated vessels as a hquid. An early appHcation was as a flame retardant for cellulose acetate safety film. It is also used in cellulose nitrate, various coatings, triacetate film and sheet, and rigid urethane foam. It has been used as a flame-retardant additive for engineering thermoplastics such as polyphenylene oxide—high impact polystyrene and ABS—polycarbonate blends. 

E. Termine and K. G. Taylor, "A New Intumescent Flame Retardant Additive for Thermoplastics and Thermosets," n Additive Approaches to PolymerModification, SPE RETEC Conference Papers, Toronto, Ontario, Canada, Sept. 1989. 

MixedPhosphona.te Esters. Unsaturated, mixed phosphonate esters have been prepared from monoesters of 1,4-cyclohexanedimethanol and unsaturated dicarboxyhc acids. Eor example, maleic anhydride reacts with this diol to form the maleate, which is treated with benzenephosphonic acid to yield an unsaturated product. These esters have been used as flame-retardant additives for thermoplastic and thermosetting resias (97). 

Nickel dialkyldithiocarbamates stabili2e vulcani2ates of epichlorhydrinethylene oxide against heat aging (178). Nickel dibutyldithiocarbamate [56377-13-0] is used as an oxidation inhibitor in synthetic elastomers. Nickel chelates of substituted acetylacetonates are flame retardants for epoxy resins (179). Nickel dicycloalkyldithiophosphinates have been proposed as flame-retardant additives for polystyrene (180—182) (see Flame retardants Heat stabilizers). 

Acrylonitrile—Butadiene—Styrene. ABS is an important commercial polymer, with numerous apphcations. In the late 1950s, ABS was produced by emulsion grafting of styrene-acrylonitrile copolymers onto polybutadiene latex particles. This method continues to be the basis for a considerable volume of ABS manufacture. More recently, ABS has also been produced by continuous mass and mass-suspension processes (237). The various products may be mechanically blended for optimizing properties and cost. Brittle SAN, toughened by SAN-grafted ethylene—propylene and acrylate mbbets, is used in outdoor apphcations. Flame retardancy of ABS is improved by chlorinated PE and other flame-retarding additives (237). 

Zinc Borates. A series of hydrated 2inc borates have been developed for use as fire-retardant additives in coatings and polymers (59,153). Worldwide consumption of these 2inc salts is several thousand metric tons per year. A substantial portion of this total is used in vinyl plastics where 2inc borates ate added alone or in combination with other fire retardants such as antimony oxide or alurnina trihydrate. 

Oil well cements are manufactured similarly to ordinary Portland cements except that the goal is usually sluggish reactivity. Eor this reason, levels of C A, C S, and alkafl sulfates are kept low. Hydration-retarding additives are also employed. 

A key property associated with chlorinated paraffins, particularly the high chlorine grades, is nonflammability, which has led to their use as fire-retardant additives and plasticizers in a wide range of polymeric materials. The fire-retardant properties are considerably enhanced by the inclusion of antimony trioxide. 

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. 

The self-extinguishing characteristics of the chlorine-containing resins are improved by incorporation of antimony oxide but this approach is not possible where translucent sheet is required. As an alternative to chlorine-based systems a number of bromine-containing resins have been prepared and, whilst claimed to be more effective, are not currently widely used. It is probably true to say that fire-retarding additives are used more commonly than polymers containing halogen groupings. 

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. 

Polyurethane foams do, however, suffer from one serious disadvantage. Unless modified they bum with copious evolution of smoke and toxic by-products, which has led to a number of fatal fires, particularly in domestic accommodation. To some extent the problem may be reduced by suitable upholstery covering, but as mentioned on p. 775 a number of countries have now made mandatory the use of fire retardent additives. At the time of writing there is considerable activity in the development of new safer systems, particularly in the use of amino materials such as melamine as additives. Further developments may also be expected in the near future. 

Calcium-sodium lignosulfonate is a better retarding additive when high concentrations of bentonite are to be used in the design of the cement slurry. 

Also sodium tetraborate (borax) and carborymethyl hydroxyethyl cellulose are used as retarding additives. 

Select the most appropriate API class of cement that meets the depth, temperature, sulfate resistance and other well limitations. Select the cement class that has a natural thickening time that most nearly meets the cementing operation time requirement, or that will require only small amounts of retarding additives. 

The effect of a flame-retardant additive on the flexural modulus provides an indication of its effect on long-time creep. 

Many plastics because they are organic are flammable incorporate flame-retardants. Additives that contain chlorine, bromine, phosphorous, metallic salts, and so forth reduce the likelihood that combustion will occur or spread. Lubricants like wax or calcium stearate reduce the viscosity of molten plastic... 

A clear demonstration of the relative importance of steric and resonance factors in radical additions to carbon-carbon double bonds can be found by considering the effect of (non-polar) substituents on the rate of attack of (nonpolar) radicals. Substituents on the double bond strongly retard addition at the substituted carbon while leaving the rate of addition to the other end essentially unaffected (for example, Table 1.3). This is in keeping with expectation if steric factors determine the regiospeeificity of addition, but contrary to expectation if resonance factors are dominant. 

Recent advances in the application of ultrafine talc for enhanced mechanical and thermal properties have been studied [12]. A particularly important use is of finely divided filler in TPO as a flame-retardant additive. In a representative formulation, 37 parts of E-plastomer, Ml 2.0, density 0.92, 60 parts of amorphous EPR, and 4 parts of fine carbon black were dry blended, kneaded at 180°C, pelletized, and press molded into test pieces, which showed oxygen index 32 versus 31 in the absence of a filler. The oxygen index is a measure of flame retardancy. 

Presence of P and N Presence of F Self-extinguishing materials. Potential flame retardant additives... 

Eastern Research Group and Syracuse Research Corporation (2005) Furniture Flame Retardancy Partnership Environmental Profiles of Chemical Flame-Retardant Additives for Low-Density Polyurethane Foam. United States Environmental Protection Agency, EPA 742-R-05-002A. 

L. Eoff. Set retarding additives, cement compositions and methods. Patent US 5264470, 1993. 

K. A. Rodrigues. Cement set retarding additives, compositions and methods. Patent US 5341881, 1994. 

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