Flame retardants phosphorus derivatives

Organophosphorus Derivatives. Neopentyl glycol treated with pyridine and phosphorus trichloride in anhydrous dioxane yields the cycHc hydrogen phosphite, 5,5-dimethyl-l,3-dioxaphosphorinane 2-oxide (2) (32,33). Compounds of this type maybe useful as flameproofing plasticizers, stabilizers, synthetic lubricants, oil additives, pesticides, or intermediates for the preparation of other organophosphoms compounds (see Flame retardants Phosphorus compounds). 

Mention has already been made of the application of alkoxycyclophos-phazenes, [NP(OR)2] , as flame retardants in rayon. Although the methoxy-derivatives, with their high phosphorus content, were expected to be most efficient in this respect, their water solubility proved a major shortcoming. However, the n-propoxy series, [NP(OPr )2] ( mainly 3—6), were found to impart excellent flame resistance and were well retained by rayon. The cyclophosphazene alkoxides were obtained by the addition of sodium-n-propoxide to the chloride homologues, (NPCl2)n, and were added to the viscose dope before the rayon was spun. The flame resistance imparted by various amino- and thioalkoxy-derivatives was also tested, but found to be inferior to the results obtained with alkoxy-deriva-tives. Several patent applications have resulted from work on this topic. ... 

Phosphorus compounds, 19 19-73 bond properties of, 19 26 chemical properties of, 19 20-31 chiral-centered, 19 25-26 economic aspects of, 19 67-69 as flame retardants, 19 51 inorganic, 11 487-488 oxidation states, coordination numbers, and geometries of, 19 20-26 as oxyacid derivatives, 19 20 reactive organic, 11 496 497 titanium in, 25 56-57 triply connected, 19 25 U.S. prices of, 19 68t U.S. production of, 19 67t... 

Ammonium polyphosphates, on the other hand, are relatively water insoluble, nonmelting solids with very high phosphorus contents (up to about 30%). There are several crystalline forms and the commercial products differ in molecular weights, particle sizes, solubilities, and so on. They are also widely used as components of intumescent paints and mastics where they function as the acid catalyst (i.e., by producing phosphoric acid upon decomposition). They are used in paints with pentaerythritol (or with a derivative of pentaerythritol) as the carbonific component and melamine as the spumific compound.22 In addition, the intumescent formulations typically contain resinous binders, pigments, and other fillers. These systems are highly efficient in flame-retarding hydroxy-lated polymers. 

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. 

Flame retardants—Whereas halogen-containing Mannich bases arc mainly used as modifiers of macromolccular materials, as mentioned before, phosphorus derivatives arc employed as additives. These products arc obtained from phosphorous acid or phosphites 584 " and from other analogous phosphorus-containing compounds. N-Heterocyclcs, after reaction with melamine and formaldehyde (585), are also used as (lame retardants. -... 

Polyphosphates derived from 4,4 -dihydric phenols or 4,4 -isopropylidenebis-phenol, bis(2,6-dibromophenol) and having an active moiety like 154 impart flame retardant properties [ W]. Thermostable polyesters were prepared by addition of bis(2-hydroxyethyl)phosphate prior to the final step of the polycondensation of ethylene glycol with dimethyl terephthalate [205]. Zinc salt of polydithiophosphate obtained by reaction of phosphorus pentasulfide with 4-substituted anisole was tested as AO in lubricating oils and greases. 

The incorporation of DOPO derivatives in DGEBA has been found to increase not only flame retardancy but also thermal stability. The DOPO-based diamine shown in Fig. 9, having a reactivity toward DGEBA intermediate between DDS and DDM, has also proved to be an effective FR. It displays a char yield (in a DEGBA/DOPO-amine) polymer of 32% at TOO C under nitrogen, compared with 13-15% for a phosphorus-free... 

His extensive career in phosphorus chemistry has emphasized topics like flame retardants for textiles and plastics, metal extractants, chelating agents, surfactants, lubricants, stabilizers for plastics, food additives, economiical processes for the synthesis of phosj orus insecticides and a considerable number of useful intermediates such as pher lphos ionous dichloride and derivatives as well as reactions leading to the formation of phosphorus-carbon bonds. 

Organophosphorus compounds (OPs) are utilized on a large scale as flame retarding agents and plasticizers in a variety of products, such as plastic materials, rubbers, varnishes, lubricants, hydraulic fluids, and other industrial applications. This family of chemicals consists of alkylated and arylated phosphate or phosphonate esters and related compounds such as phosphites, phosphines, and related dimeric forms as well as ionic forms (Figure 31.2). " The low volatility of phosphoric acid and derivatives makes it the preferred choice of the phosphorus based FRs. These FRs are most effective in polymers that char readily. Also halogenated phosphate esters, such as tris(l-chloroisopropyl) phosphate (TCPP), and tris(2-chloroethyl) phosphate (TCEP), are widely used. These combine the properties of both the halogen and the phosphorus compounds. 

Uses Plasticizer, flame retardant for plastics incl. acrylics, ceiiuiosics, epoxy, nitrile, phenolic, thermoset po ester, PP, PS, PVAc, PVC, clear vinyl films, vinyl-coated fabrics, flexible PU foam, syn. rubber, wire/ cable insulation, plastisols plasticizer, coalescing agent for coatings Manuf./Dlstrlb. Akzo Nobel FMC Rhodia/Phosphorus Perf. Derivs. Trade Names Antiblaze 519... 

Dimelamine phosphate CAS 56974-60-8 Empihcal C6H15N12O4P Properties Wh. powd. sol. 2 g/l in water m.w. 350.24 dens. 1.66 kg/l dec. 300 C Uses Flame retardant for polymers, intumescent paints/coatings, plastics (polyesters, polymethyl methacrylate, polyolefins, PS, PU foams), textiles, paper intumescent paint/mastic ingred. catalyst in intumescent systems Manuf/Distrib. DSM Chem. N. Am. http //www. dsmna. com Trade Name Synonyms Amgard ND t[Rhodia/Phosphorus Perf. Derivs. 

Uses Flame retardant for rigid urethane foams, unsat. polyester resins, waterborne latexes vise, depressant and flame retardant in ATH-filled polyester resins intermediate for other flame retardants as solvent Manuf./Distrib. Aceto http //www.aceto.com, Akzo Nobel http //www.akzonobel.com, Aldrich http //WWW. sigma-aldrich. corn, FI u ka http //www.sigma-aldrich.com. Focus Rhodia/Phosphorus Perf. Derivs. http //WWW. rhodia-ppd. com Trade Name Synonyms Amgard DMMP [Rhodia/Phosphorus Perf. Derivs. http //www.rhodia-ppd.com]. Antiblaze DMMP [Rhodia/Phosphorus Perf. Derivs. 

Stackman [29] carried out a study to find systems suitable for reducing the flammability of polyethylene terephthalate (PET) and poly-1,4-butylene terephthalate (PBT) while retaining the chemical and physical properties of the original polymers. The additives used were phosphine oxides, phosphonates and phosphates and their activity was assessed by means of an oxygen index test. Most of the phosphorus esters were found to be volatile under the blending conditions and both the halogenated phosphorus esters and halogenated derivatives of phosphorus oxide proved to be ineffective as flame retardants. 

The properties of polymers are hardly affected by the incorporation of phosphorus. Diesters of H-phosphonic acid and their inunediate derivatives have found a number of applications in polymer synthesis such as flame retardants, antioxidants, heat and Ught stabilizers, catalysts, degrading agents, and alkylating agents. They are also used as corrosion inhibitors, scale inhibitors, and lubricants (antiwear and load-carrying additives). 

The formation of unsaturated polyphosphoesters via acyclic diene metathesis pol5nnerization has been described (90). The ADMET copol5m erization of a phosphorus based a,(u-diene with different amounts of a castor oil derived diene has been exemplified. These pol3nner types show a good flame retardancy. The synthesis of a di-lO-undecenoylglycerol mixture is shown in Figure 4.16. 

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