Flame-retardancy additives

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). 

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. 

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... 

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. 

Figure 10.2 Chemical stmcture of a UV-stable nonhalo-genated iV-alkoxy-hindered amine flame-retardant additive (Flamestab NOR 116) for polyolefins (Ciba Specialty Chemicals)...

The antimony oxide/organohalogen synergism in flame retardant additives has been the subject of considerable research and discussion over the past twenty-five years (1-17). In addition to antimony oxide, a variety of bismuth compounds and molybdenum oxide have been the subject of similar studies (18-20). Despite this intensive investigation, relatively little has been conclusively established about the solid state chemical mechanisms of the metal component volatilization, except in those cases where the organohalogen component is capable of undergoing extensive intramolecular dehydrohalogenation. 

Finally, the results reported here clearly demonstrate the utility of utilizing the flame retardant additives as sensitive probes into studying the course of the solid state chemistry which occurs during pyrolysis. 

Nonwoven products ranging from medical disposables to automotive fabrics are required to meet specific flammability standards. These fabrics are generally composed of cellulosic and/or synthetic fibers which are flammable. Additionally, polymer coatings are applied to the fabric to impart properties such as strength, abrasion resistance and overall binding. It is the purpose of this paper to describe the various polymer coatings commonly used in the nonwovens industry and their effect on flammability of the substrates. Additionally, the effect of flame retardant additives, commonly used in latex formulations, will be discussed. 

PMMA - Red Phosphorus System. The initial reaction that was investigated was that between PMMA and red phosphorus (4-51. Phosphorus was chosen since this material is known to function as a flame retardant for oxygen-containing polymers (1 2). Two previous investigations of the reaction of PMMA with red phosphorus have been carried out and the results are conflicting. Raley has reported that the addition of organic halides and red phosphorus to PMMA caused moderate to severe deterioration in flammability characteristics. Other authors have reported that the addition of chlorine and phosphorus compounds are effective flame retardant additives (12). 

Char formation and reduced monomer production are observed for all of these additives upon reaction with PMMA. Char formation increases as a function of temperature, for the hydrido cobalt compound, there is 5% char at 262°, 8.5% at 322°, 15% at 338°, and 19% at 375°C the cobalt(lll) cyanide produces 3% char at 338° and 11% at 375°C the cobalt(ll) cyanide yields 11% char at 375°C. At the highest temperature, 375°C, the amount of monomer formation is 22% for K3Co(CN)5, 11% for K3Co(CN)6, and 10% for HCo[P(OPh)3]4. Ideally one would hope to observe no monomer formation and complete char production. Such is not the case here, these materials probably have no utility as flame retardant additives for PMMA since monomer formation, even at a reduced level, will still permit a propagation of the burning process. While somewhat positive results for these three additives do not prove the validity of the hypothesis, we take this to be a starting point in our search for suitable additives, further work is underway to refine the hypothesis and to identify other potential hydrogenation catalysts and other additives that may prove useful as flame retardants for PMMA... 

In this paper we have presented evidence to show that it is quite feasible to determine the detailed course of reaction between a polymer and an additive. Further, the understanding of this reaction pathway provides insight into new additives and schemes for the identification of efficacious flame retardant additives. Finally, we have elucidated schemes for the cross-linking of PMMA and have shown that the schemes do provide a route for flame retardation. It is imperative to realize that the purpose of this work is not to directly develop new flame retardants, rather the purpose is to expose the chemistry that occurs when a polymer and an additive react. This exposition of chemistry continually provides a new starting point for further investigations. The more that pathways for polymeric reactions are determined the more information is available to design suitable additives to prevent degradation of polymers. 

The advantage of using a paste dispersion of a flame-retardant additive in this polyester resin formulation is evident from the... 

Blends of flame retardant additives have been advocated as an approach to an optimum balance of properties in the finished products. For example, blends of tetrabromophthalate esters with de-cabromodiphenyl oxide or other flame retardants are reported to yield a V-0 rating in modified PPO and in polycarbonate resins without compromising melt processability or performance properties (23a-b). 

An example of a direct comparison of performance properties with and without added flame retardants for "New ignition resistant polycarbonate resins" is provided in a paper by workers at the Dow Chemical Company (32). The technology of the flame retardant additives is de scribed as including... 

The flame retardant performance of various flame retardant additives in a commercial polycarbonate/ABS alloy were compared. No antimony oxide was required. The data shows brominated phosphate to be a highly efficient flame retardant in this alloy (Table XI). An alloy composition containing 14% brominated phosphate and no antimony oxide gives a V-0 rating (Table XII). The melt index of this alloy containing 12% brominated polystyrene was 7.6 g/10 min. (at 250°C) the equivalent resin containing brominated phosphate had a melt index of 13.3 g/10 min. 

Mirex and chlordecone are no longer made or used in the United States. Mirex and chlordecone were most commonly used in the 1960s and 1970s. Mirex was used as a pesticide to control fire ants mostly in the southeastern part of the United States. It was also used extensively as a flame retardant additive under the trade name Dechlorane in plastics, rubber, paint, paper, and electrical goods from 1959 to 1972 because it does burn easily. Chlordecone was used to control insects that attacked bananas, citrus trees with no fruits, tobacco, and ornamental shrubs. It was also used in household products such as ant and roach traps. Chlordecone is also known by its trade name Kepone . All registered products containing mirex and chlordecone were canceled in the United States between 1977 and 1978. 

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