Additives for flame retardancy

Viscose spinning bath additive for flame-retardant rayon. 

Wool has been regarded as a relatively safe fiber from the flammability point of view. However, it could be flame retarded to a higher degree if required. Hendrix et al. (26) suggested a large improvement in fire resistance of wool by treatment with 15% H PO. Beck et al. (27) showed that weak acidic materials, such as boric acid and dihydrogen phosphate, are effective additives for flame retarding wool by the condensed-phase mechanism (increased char residue). 

Z. Nir, Y. Bar-Yaacov, R. Minke, I. Touval, D. A. Kourtides and J. A. Parker, A new brominated polymeric additive for flame retardant glass-filled PBT, /. Fire. Retardant Chem., 9 181-188, 1982. 

In addition to dyeabiHty, polyesters with a high percentage of comonomer to reduce the melting poiat have found use as fusible biader fibers ia nonwoven fabrics (32,34,35). Specially designed copolymers have also been evaluated for flame-retardant PET fibers (36,37). 

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. 

Flame Retardants. Bromine compounds make up an important segment of the market for flame retardants used in polymers. Additive flame retardants are added to polymers during processing reactive flame retardants react chemically to become part of the polymer chain itself. In addition to the compounds Hsted in Table 3, a number of proprietary mixtures and phosphoms—bromine-containing flame retardants are also sold (see Elame RETARDANTS, HALOGENATED, FLAAffi RETARDANTS). 

Most circuit boards are FR-4 boards that meet standards for fire safety by the use of brominated epoxy resins in which the reactive flame-retardant tetrabromobisphenol A (TBBPA) forms part of the polymeric backbone of the resin. Alternative flame-retardant materials are used in only 3-5 per cent of the FR-4 boards, but additional alternative flame-retardant materials are also imder development. Little information exists concerning the potential environmental and human health impacts of the materials which are being developed as alternatives to those used today that are based on brominated epoxy resins. 

Applications The general applications of XRD comprise routine phase identification, quantitative analysis, compositional studies of crystalline solid compounds, texture and residual stress analysis, high-and low-temperature studies, low-angle analysis, films, etc. Single-crystal X-ray diffraction has been used for detailed structural analysis of many pure polymer additives (antioxidants, flame retardants, plasticisers, fillers, pigments and dyes, etc.) and for conformational analysis. A variety of analytical techniques are used to identify and classify different crystal polymorphs, notably XRD, microscopy, DSC, FTIR and NIRS. A comprehensive review of the analytical techniques employed for the analysis of polymorphs has been compiled [324]. The Rietveld method has been used to model a mineral-filled PPS compound [325]. 

Air Products, a manufacture of latex binders, has completed a comprehensive study of flame retardants for latex binder systems. This study evaluates the inherent flammability of the major polymer types used as nonwovens binders. In addition, 18 of the most common flame retardants from several classes of materials were evaluated on polyester and rayon substrates. Two of the most widely recognized and stringent small scale tests, the NFPA 701 vertical burn test and the MVSS-302 horizontal burn test, are employed to measure flame retardancy of a latex binder-flame retardant system. Quantitative results of the study indicate clear-cut choices of latex binders for flame retardant nonwoven substrates, as well as the most effective binder-flame retardant combinations available. 

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. 

Generally, flame retardants for engineering PET compositions are based on bromine-containing compounds (such as brominated polycarbonate, decabro-modiphenyl oxide, brominated acrylic, brominated polystyrene, etc.). Such compounds are available commercially (such as from the Ethyl Chemical Corporation, Great Lakes Chemical Corporation, Dead Sea Bromine Company, etc.) In addition, the flame-retardant package generally contains a synergist, typically sodium antimonate. PET may also be flame-retarded with diarylphosphonate, melamine cyanurate or red phosphorus. 

Phosphorus trichloride, PC13, and phosphorus pentachloride, PCl5, are the two most important halides of phosphorus. The former is prepared by direct chlorination of phosphorus. Phosphorus trichloride, a liquid, is a major intermediate for the production of pesticides, oil additives, and flame retardants. Phosphorus pentachloride, a solid, is made by allowing the trichloride to react with more chlorine (recall Fig. 2.8). 

Among the emerging pollutants of industrial origin, Bisphenol A [2,2 bis(4-hydroxydiphenyl)pro-pane] (BPA) has special relevance since it was one of the first chemicals discovered to mimic estrogens as endocrine disrupters.147 This compound was first reported by Dianin in 1891.1411 BPA is produced in large quantities worldwide, mainly for the preparation of polycarbonates, epoxy resins, and unsaturated polyester-styrene resins.149 The final products are used in many ways, such as coatings on cans, powder paints, additives in thermal paper, in dental composite fillings, and even as antioxidants in plasticizers or polymerization inhibitors in polyvinyl chloride (PVC). To a minor extent, BPA is also used as precursor for flame retardants such as tetrabromobisphenol A or tetrabromobisphenol-S-bis(2,3-dibromopropyl) ether.150 This substance can enter the environment... 

WEEE has had a direct affect on flame-retardant use, because flame retardants are used in almost all electrical and electronic equipment to prevent fires from short circuits. This directive lays down rules for disposal and recycling of all electrical and electronic equipment that goes back to the previous incinerator discussion. For flame retardants, this directive affects how the plastic parts, cable jackets, and enclosures are flame retarded. If the plastic cannot be reground and recycled, it must go to the incinerator, in which case it cannot form toxic by-products during incineration. This has led to the rapid deselection of brominated FR additives in European plastics that are used in electronics, or the complete removal of FR additives from plastics used in electronics in Europe. This led, in turn, to increases in electrical fires in Europe, and now customers and fire-safety experts demand low environmental impact and fire safety. However, the existing nonhalogen flame-retardant solutions brought in to replace bromine have their own balance-of-property issues, and so research continues to develop materials that can meet WEEE objectives. 

After PVC, polyolefin copolymers, predominantly polyethylene copolymers, are the next most widely used material for FR applications in wire and cable. Polyethylenes have very good dielectric strength, volume resistivity, mechanical strength, low temperature flexibility, and water resistance. In contrast to PVC, polyolefins are not inherently FR and thus are more highly formulated, requiring the addition of FRs to meet market requirements for flame retardancy. For this reason, and because of the steady global trend toward halogen-free materials for wire and cable applications, more space will be devoted to this section on FR polyolefins compared with the above discussion of PVC. 

Mono- and diphosphonium halides have been found to be flame retardants for plastic materials. Their effectiveness can be related to the formation of various active phosphorus compounds, as well as to many of the postulated mechanisms for flame retardant action. The compounds are postulated to be effective because they decompose on ignition to thermally stable phosphine oxides or phosphonic acids which, in turn, are decomposed to continuous films of phosphate glass. In addition, the phosphonium halides form alkyl halides which cool the flame and/or form halogen acids which are fame retardants. 

Details are given of the addition of flame retardant and smoke suppressant additives to PVC to meet specifications such as oxygen index, heat release, smoke evolution or extent of burning in cable tests. Data are presented for synergistic combinations of additives in PVC formulations. 31 refs. 

For quantitative determination of the rate and the amount of heat release, we have developed a method based on complete combustion of the volatiles on a platinum catalyst and measurement of amount of oxygen required (J8). The required oxygen is generated by a reaction coulometer (Figure 27) and is related to the heat of combustion as shown in Figure 28. As discussed in Chapter 14, the amount of combustible, volatile pyrolysis products formed and the rate of heat release may be reduced drastically by the addition of flame retardants. 

The addition of flame retardants, either additive or reactive types, can provide flame-retardant foams having low flame spread or surface flammability, but flame retardants do not improve the temperature resistance of these foams because the thermal stability or the dissociation temperature of the urethane linkage is relatively low and unchanged by the addition of flame retardants, i.e., the linkage dissociates at about 200°C to form the original components in polyol and polyisocyanate. The dissociation can result in further decomposition of polyol and polyisocyanate into low-molecular-weight compounds at elevated temperatures. For these reasons urethane foams are not temperature-resistant nor thermally stable. 

These results give further impetus to our belief that a variety of additives may be more effectively delivered to polymer films and fibers as high melting inclusion compounds formed with CDs. In this connection for flame retardants, which can be toxic and mutagenic on contact, their confinement in CD-ICs not only protects them from the environment, but protects the wearer of fabrics containing embedded FR-CD-ICs from direct contact with the FR. Thus, one can envision the use of the most effective FRs with little regard to issues of FR toxicity, if they are delivered in the form of their CD-ICs. 

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