FYROL Flame Retardants

In the field of industrial chemicals, among others. Dr. Toy and his associates pioneered Stauffer Chemical Company s Fyrol flame retardants and were instrumental in the generation of new flame retardant plasticizers like the Fhosflex types and new industrial hydraulic fluids such as the Fyrquel and Fyrgard series. Most of these products have attained annual production volumes in excess of one million pounds. 

HOCH2 - P [(OCH2 - CH2)n OHI2 Fyrol HM Figure 14. Fyrol flame retardants... 

Several appHcations have been found for bis(2-chloroethyl) vinylphosphonate as a comonomer imparting flame retardancy for textiles and specialty wood and paper appHcations. Its copolymerization characteristics have been reviewed (76,109). This monomer can be hydrolyzed by concentrated hydrochloric acid to vinylphosphonic acid, polymers of which have photoHthographic plate coating utiHty (see Lithography). It is also an intermediate for the preparation of an oligomeric vinylphosphonate textile finish, Akzo s Fyrol 76 [41222-33-7] (110). 

Ra.dia.tlon. Use of radiation to affect fixation of some flame retardants is being investigated (110). Electron-beam fixation requires the selection of compounds that can be insolubilized inside or outside of the fiber with high yield in a short time. Polyunsaturated compounds, eg, Fyrol 76, have shown promise (see Radiation curing). 

THPOH-NH andFyrol76. The THPOH—NH finish and the Fyrol 76 finish also impart flame retardancy to certain polyester—cotton blends if the blends contain at least 65% cotton. 

Flame retardants (qv) are incorporated into the formulations in amounts necessary to satisfy existing requirements. Reactive-type diols, such as A/ A/-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol 6), are preferred, but nonreactive phosphates (Fyrol CEF, Fyrol PCF) are also used. Often, the necessary results are achieved using mineral fillers, such as alumina trihydrate or melamine. Melamine melts away from the flame and forms both a nonflammable gaseous environment and a molten barrier that helps to isolate the combustible polyurethane foam from the flame. Alumina trihydrate releases water of hydration to cool the flame, forming a noncombustible inorganic protective char at the flame front. Flame-resistant upholstery fabric or liners are also used (27). 

Fyrol 76 [41222-33-7] - [FLAME RETARD ANTS - PHOSPHORUS FLAME RETARDANTS] (Vol 10)... 

Flame relardanls are used in smolder-resistant upholstery fabric, combination flame retardant-durable press performance, flame-retardant treatments for wool, thermoplastic fibers (Tris. decabromodiphenyl oxide-polyacrylate finishes. Antihlu/e 19. nylon finishes), polyester-cotton fiber blends (THPOH-ummonju-Tris finish, decabromodiphenyl oxide-polyacrylate finish. THPC-amide-polytv illy I bromide) finish, THPOH-NHi and Fyrol 76. LRC-UX) finish, phusphonium salt-urea precondcn-satej. cotton-wool blends, and core-yam fabric,... 

Several commercial products have resulted from our phosphorus oligomer research. Fyrol 99, a 2-chloroethyl ethylene phosphate oligomer, has been successfully used as a flame retardant additive in rebonded urethane foam, in thermoset resins, in intumes-cent coatings, adhesives, paper air filters (13), and related uses. This product is less volatile and has a higher flame retardant efficacy than the parent compound tris(2-chloroethyl) phosphate. A related product was developed especially for use in flexible polyurethane foams. A vinylphosphonate/methylphospho-... 

The major commercial alternative to DOPO and its derivatives for reactively flame retarding epoxy resins, especially for electronic applications, is an oligo(l,3-phenylene methylphosphonate) (Structure 5.18) marketed by Supresta under the tradename Fyrol PMP. Fyrol PMP has a functionality higher than that of DOPO and can be used either as a hardener (curing agent) or be precondensed with an epoxy. 

At Bolton, we also have attempted to introduce volatile and possible vapor phase-active, phosphorus-based FR components in back-coating formulations.60 62 The selected FRs included tributyl phosphate (TBP), a monomeric cyclic phosphate Antiblaze CU (Rhodia Specialties) and the oligomeric phosphate-phosphonate Fyrol 51 (Akzo). When combined with an intumescent char-forming pentaerythritol (PER) derivative (NH1197, Chemtura) and applied as a back-coating on to cotton and polypropylene substrates, significant improvements in overall flame retardancy were observed. 

SYNS CELLUFLEX FYROL CEF NCI-C60128 NIAX FLAME RETARDANT 3 CF TRICHLORETHYL PHOSPHATE TRI-P-CHLOROETHYL PHOSPHATE TRI(2-CHLOROETHYL)PHOSPHATE TRIS(2-CHLOROETHYL)ESTER PHOSPHORIC ACID TRIS(p-CHLOROETHYL) PHOSPHATE TRIS(2-CHLOROETH-YL) PHOSPHATE... 

Also, later in this paper, when we discuss the reaction of ethylene oxide with the pyrophosphate bond, there will be presented evidence addressing the level of pyrophosphate content believed present in Vircol 82. Fyrol 6, although produced commercially through processes other than those described in this slide, continues to be a commercially useful flame retardant for rigid urethane foams. 

Figure 1. Vlrcol 82 and Fyrol 6. Two commercial flame retardants for rigid urethane foams. (1, 2)...

One of the important commercial flame retardants for plastics, the phosphorus-containing oligomer Fyrol 99, is prepared by the condensation of tris -(2-chloroethyl) phosphate, as shown in Fig. 

Fyrol 76 is a reactive, curable flame retardant for textiles, in p>articular for cotton fabric (27, 28), vhere it co-reacts with N-methylol-acrylamide in the presence of a free radical catalyst such as a persulfate. In the 70 s the applicatiai of Fyrol 76 was one of the most oommcxi methods to obtain flame-proof cotton, vhich was utilized, for example, by Cone Mills CorpxDration for the manufacture of flame-proof p>ajamas for children. 

In 1976, the US market for flame retardants applied to cotton was estimated at 2 million Ib./year. Presumably, about half of this amount was attributed to Fyrol 76. 

Further important ccranercial flame retardants, developed by associates of Dr. Toy are Fyrol 99 (non-reactive for soft polyurethane foams) as well as halogen-free compounds like Fyrol 51 e.g. for polyurethanes or Fyrol HMP for the fire-protection of automotive air filters (29). In the application for polymer films, in addition to flame protection, Fyrol HMP was (new Victastab HMP) found to enhance the tensile strength of Mylar polyester films considerably. 

Fyrol HMP (equation 28) passed our tests as a flame retardant but we didn t... 

Cotton flannels treated with the Fyrol 76 system retain acceptable softness and strength. The flame-retardant property is not adversely affected after 50 wash and dry cycles using perborate bleach. We had expected Fyrol 76 to be an assured commercial success. Unfortunately, everybody likes to have flame retarded children s pajamas to protect their children from accidental burning, but they are unwilling to pay a little extra for such protection. However, Dr. Weil informed me that recently there is revived commercial interest in Fyrol 76. 

This listing of chain extenders or cross-linkers is obviously incomplete since many other types of chain extenders may be used where special end use requirements may have to be met, for example, for flame retardance. In this case, halogenated diols, for example, 2,3-dibromo-2-butane-l,4-diol (GAF Corp.), or phosphate or phosphonate group-containing diols, for example, Fyrol 6 (Stauffer Chemical Co.), may be used. 

Fyrol . [Akzo Akzo Chem. BV] Phosphate derivs. organic flame retardant for urethane foams, thermosetting and thermoplastic resins, coatings. 

Bellstein Handbook Reference) AI3-08678 BRN 0878263 CCRIS 876 DImethoxymethyl-phosphIne oxide Dimethyl methanephosphonate Di-methyl methylphosphonate DMMP EINECS 212-062-3 Fyrol DMMP HSDB 2590 Methyl phosphonic acid, dimethyl ester NCI-C54762 NSC 62240 Phosphonic add, methyl-, dimethyl ester Pyrol dmmp. Flame retardant for applications where high phosphorus content, good solvency, and low viscosity are desired lowers viscosity of epoxy resins and unsaturated polyesters filled with hydrated alumina oxide. Liquid bp = 181 , bp20 = 79.6" d ° = 1.4099 Am = 217 nm (e = 13, EtOH) soluble in H2O, Et20, EtOH LDsO (rat orl) > 5000 mg/kg. Akzo Chemie. 

Antiblaze 80 AP 33 2-Chloro-1-propanol phosphate (3 1) EINECS 228-1504 Fyrol PCF NSC 524664 1-Propanol, 2-chloro-, phosphate (3 1) Tris(P-chloropropyl) phosphate Tris(2-chloropropyl) phosphate. Flame retardant. 

Uses Flame retardant for PU foams, unsat. polyester, liq. phenolic resins flame retardant formerly used in children s sleepwear Manuf./Distrib. Sinochem Jiangsu Wuxi http //www.sinochemwuxi. com Trade Name Synonyms Fyrol 38 [Akzo Nobel http //www.akzonobel.com], Fyrol FR-2 [Akzo Nobel http //www.akzonobel.com]... 

Dimethyi Methyiphosphonate (DMMP) [756-79-6]. This is a water-soluble liquid, bp 185°C, with the formula CH3P(=0)(0CH3)2, contains 25% phosphorus, which is near the maximum possible for a phosphorus ester, and therefore highly efficient as a flame retardant. It is sold by Akzo Nobel as FYROL DMMR Applications include use as a viscosity depressant and flame retardant in alumina trihydrate (ATH)-filled polyester resins (66) such as used for bathtubs and shower stalls. Some applications have been found in rigid polyurethane foams and as an intermediate for making other flame retardants. In Europe, DMMP has an R46 (mutagen) classification, which deters its use. 

Oligomeric 2-Chloroethyl Phosphate. Akzo Nobel s FYROL 99 [109640-81-5] (82,83) is low in volatility and useful in resin-impregnated air filters, in flexible urethane foam, rehonded foam, structural foam and flame-retardant coatings. 

FYROL 51 is a water-soluble liquid containing about 21% phosphorus. The end groups are principally primary hydroxyl and the compound can thus be incorporated chemically into aminoplasts, phenolic resins, and polyurethanes. FYROL 51, or 58 (diluted) is used with amino resins to produce a flame-retardant resin flnish on paper used for automotive air filters, or for backcoating of upholstery fabric to pass the British or California flammability standards. Under the trade name FYROLTEX HP (Akzo Nobel), it has been in development for cotton textile finishing, in combination with an amino resin (117). 

By inclusion of a limited amount of water or alcohol in the synthesis, oligomers of this type can be made with controlled hydroxyl content. Such products are exemplified by Akzo Nobel s Fyrol 51 or Fyrol 58 flame retardants which are useful as reactive oligomers in thermosets. In resin-treated automotive air filters this type of product is chemically linked into the resin and resists leaching by water when the filters are cleaned. Fyrol 51 has also found utility in making flame-retarded polyurethanes and textile flnishes. 

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