Flame retardants combinations

Ethylene vinyl acetate (EVA) polymers are used in thermoplastic and thermosetting jacketing compounds for apphcations that require flame retardancy combined with low smoke emission during the fire as well as the absence of halogen in the composition. 

Phosphorus -bromine flame retardant synergy was demonstrated in a 2/1 polycarbonate/polyethylene blend. These data also show phosphorus to be about ten times more effective than bromine in this blend. Brominated phosphates, where both bromine and phosphorus are in the same molecule, were also studied. In at least one case, synergy is further enhanced when both phosphorus and bromine are in the same molecule as compared with a physical blend of a phosphorus and a bromine compound. On a weight basis, phosphorus and bromine in the same molecule are perhaps the most efficient flame retardant combination. The effect of adding an impact modifier was also shown. 

Phosphorus/bromine combinations are perhaps the most effective flame retardant combination (ref. 3) and claims have been made for synergy. The formation of phosphorus trichloride or oxychloride has been postulated by analogy to that of the formation of antimony trichloride and oxychloride but there is no evidence for this mechanism. Some reports of synergy appear to be a result of a nonlinear response to the flame retardant concentration. 

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. 

Another experimental program was conducted with binder-flame retardant combinations on rando-rayon. The eighteen flame retardants were paired with a latex binder and screened for performance in an NFPA-701 flame retardant test. Seven of the best performing flame retardants were chosen for further study. Additionally, since all seven happened to be non-durable, the best performing durable flame retardant was added at a higher add-on and flame retardant level. 

S. Zhang, A.R. Horrocks, T.R. Hull, and B.K. Kandola, Flammability, degradation and structural characterization of fiber-forming polypropylene containing nanoclay-flame retardant combinations, Polym. Degrad. Stabil., 2006, 91 719-725. 

In EPR formulations, calcium borate was found to be a good replacement for the combination of antimony trioxide with an organic flame retardant Calcium borate, in addition to affecting flame retardation, also reinforces the polymer. Another alternative is based on huntite/hydromagnesite filler. Here, some antimony trioxide and organic flame retardant combination must be added. The huntite/magnesite filler combination cannot, by itself, halt flame spread. ... 

Although, for the photolytically degrading halogenated flame-retardants combinations of absorbers and HALS might give sufficient stability [108], in combination with a flame-retardant several other UV stabilizer types can outperform HALS. The development of less basic NOR HALS types can change this situation. These types are less deactivated, causing that in combination with flame-retardants they can outperform all other stabilizers [103,108]. 

Ramirez-Vargas E, Sanchez-Valdes S, Parra-Tabla O, Castaneda-Gutierrez S, Mendez-Nonell J, Ramos-deValle LF, Lopez-Leon A, Lujan-Acosta R (2012) Structural characterization of LDPE/EVA blends containing nanoclay-flame retardant combinations. J Appl Polym Sci 123 1125-1136... 

Subsequent hydrolysis produces P2O3 or H3PO4. When triphenyl phosphine oxide is used, P2-, PO-, P02-, and small amounts of P- and HPO- are found in zone 3 of the flame and can react with active radicals directly in that zone [28]. The synergetic effect of flame-retardant combinations containing phosphorus and a halogen may still be increased by the reaction between degradation products that are formed in the pyrolysis zone [29]. The HCl formed by the decomposition of the halide... 

The brominated flame retardants can cause catastrophic deactivation of the HAS [78]. In formulations containing aromatic brominated flame retardants, combination of UV absorbers and a new class of siloxan with HAS provide the highest level of UV stabilization. Dyes influence also PO photostability [79]. 

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. 

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. 

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. 

In polymers such as polystyrene that do not readily undergo charring, phosphoms-based flame retardants tend to be less effective, and such polymers are often flame retarded by antimony—halogen combinations (see Styrene). However, even in such noncharring polymers, phosphoms additives exhibit some activity that suggests at least one other mode of action. Phosphoms compounds may produce a barrier layer of polyphosphoric acid on the burning polymer (4,5). Phosphoms-based flame retardants are more effective in styrenic polymers blended with a char-forming polymer such as polyphenylene oxide or polycarbonate. 

Antagonism between antimony oxide and phosphoms flame retardants has been reported in several polymer systems, and has been explained on the basis of phosphoms interfering with the formation or volatilization of antimony haUdes, perhaps by forming antimony phosphate (12,13). This phenomenon is also not universal, and depends on the relative amounts of antimony and phosphoms. Some useful commercial poly(vinyl chloride) (PVC) formulations have been described for antimony oxide and triaryl phosphates (42). Combinations of antimony oxide, halogen compounds, and phosphates have also been found useful in commercial flexible urethane foams (43). 

Related esters of this alcohol are disclosed by Ak2o as useflil flame retardants for polypropylene, particularly in combination with ammonium polyphosphate (90). 

Usage of phosphoms-based flame retardants for 1994 in the United States has been projected to be 150 million (168). The largest volume use maybe in plasticized vinyl. Other use areas for phosphoms flame retardants are flexible urethane foams, polyester resins and other thermoset resins, adhesives, textiles, polycarbonate—ABS blends, and some other thermoplastics. Development efforts are well advanced to find appHcations for phosphoms flame retardants, especially ammonium polyphosphate combinations, in polyolefins, and red phosphoms in nylons. Interest is strong in finding phosphoms-based alternatives to those halogen-containing systems which have encountered environmental opposition, especially in Europe. 

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. 

Combination Flame Retardant—Durable Press Performance. Systems using THPC, urea, and TMM can be formulated to give fabrics which combine both flame-retardant performance and increased wrinkle recovery values (80). Another system employs dimethylol cyanoguanidine with THPC under acidic conditions (115). Both of these systems lead to substantial losses in fabric tensile and tearing strength. 

Another approach to durable press—flame retardancy uses a combination of a cross-linking system, antimony(III) oxide, and a bromine-containing reactive additive, namely dibromoneopentyl glycol, to achieve dual properties (120,121). 

Phosphonium Salt—Urea Precondensate. A combination approach for producing flame-retardant cotton-synthetic blends has been developed based on the use of a phosphonium salt—urea precondensate (145). The precondensate is appUed to the blend fabric from aqueous solution. The fabric is dried, cured with ammonia gas, and then oxidized. This forms a flame-resistant polymer on and in the cotton fibers of the component. The synthetic component is then treated with either a cycUc phosphonate ester such as Antiblaze 19/ 19T, or hexabromocyclododecane. The result is a blended textile with good flame resistance. Another patent has appeared in which various modifications of the original process have been claimed (146). Although a few finishers have begun to use this process on blended textiles, it is too early to judge its impact on the industry. 

Additives. Because of their versatility, imparted via chemical modification, the appHcations of ethyleneimine encompass the entire additive sector. The addition of PEI to PVC plastisols increases the adhesion of the coatings by selective adsorption at the substrate surface (410). PEI derivatives are also used as adhesion promoters in paper coating (411). The adducts formed from fatty alcohol epoxides and PEI are used as dispersants and emulsifiers (412). They are able to control the viscosity of dispersions, and thus faciHtate transport in pipe systems (413). Eatty acid derivatives of PEI are even able to control the viscosity of pigment dispersions (414). The high nitrogen content of PEIs has a flame-retardant effect. This property is used, in combination with phosphoms compounds, for providing wood panels (415), ceUulose (416), or polymer blends (417,418) with a flame-retardant finish. 

Flame retardants such as a-alumina trihydrate [14762-49-3] can be added to latex-based foamed carpet backing a combination of antimony oxide [1309-64-4] and chlorinated paraffins is used in dry mbber. 

Sulfamic acid has a unique combination of properties that makes it particularly well suited for scale removal and chemical cleaning operations, the main commercial appHcations. Sulfamic acid is also used in sulfation reactions, pH adjustment, preparation of synthetic sweeteners (qv), and a variety of chemical processing appHcations. Salts of sulfamic acid are used in electroplating (qv) and electroforrning operations as well as for manufacturing flame retardants (qv) and weed and hnish killers (see Herbicides). 

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