Polyamides, additives Flame retardants

Additives used in final products Plasticizers/flexibilizers epoxidized oils, low molecular polyamides, polysulfidesdibutyl phthalate, condensation products of adipic acid and glycols, isodecyl pelargonate, cyclohexyl pyr-rolidone Other diluents (glycide ether), modifiers, rheological additives, flame retardants Antistatics alkyl dipolyoxyethylene ethyl ammonium ethyl sulfate, carbon black, carbon monofiber, graphite, quaternary ammonium compound, silver-coated basalt, tin oxide Release calcium carbonate, carnauba wax, ceramic microspheres, ethylene bis stearoformamide, montan wax, silicone oil Slip carbon fiber, PTFE, sorbitan tristearate ... 

Nylon. Nylons comprise a large family of polyamides with a variety of chemical compositions (234,286,287). They have excellent mechanical properties, as well as abrasion and chemical resistance. However, because of the need for improved performance, many commercial nylon resins are modified by additives so as to improve toughness, heat fabrication, stabiUty, flame retardancy, and other properties. 

The use of copolymers is essentially a new concept free from low-MW additives. However, a random copolymer, which includes additive functions in the chain, usually results in a relatively costly solution yet industrial examples have been reported (Borealis, Union Carbide). Locking a flame-retardant function into the polymer backbone prevents migration. Organophosphorous functionalities have been incorporated in polyamide backbones to modify thermal behaviour [56]. The materials have potential for use as fire-retardant materials and as high-MW fire-retardant additives for commercially available polymers. The current drive for incorporation of FR functionality within a given polymer, either by blending or copolymerisation, reduces the risk of evolution of toxic species within the smoke of burning materials [57]. Also, a UVA moiety has been introduced in the polymer backbone as one of the co-monomers (e.g. 2,4-dihydroxybenzophenone-formaldehyde resin, DHBF). 

The red allotropic form of phosphorus is relatively nontoxic and, unlike white phosphorus, is not spontaneously flammable. Red phosphorus is, however, easily ignited. It is a polymeric form of phosphorus, thermally stable up to ca. 450°C. In its finally divided form, it has proved to be a powerful flame-retardant additive.18 Elemental red phosphorus is a highly efficient flame retardant, especially for oxygen-containing polymers such as polycarbonates and polyethylene terephthalate). Red phosphorus is particularly useful in glass-filled polyamide 6,6, where high processing temperature (about 280°C) excludes the use of most phosphorus compounds.19 In addition, coated red phosphorus is used to flame retard nylon electrical parts, mainly in Europe and Asia.20... 

Polyamides It is very difficult to incorporate additives in polyamides because of their melt reactivities. The recent developments for the flame retardancy of polyamides concern mainly the inclusion of nanoparticles, discussed in Section 24.5.3. 

Red phosphorus (RP) is a component of matchbox strike plates and is used as an ingredient in certain commercial rat and cockroach poisons. RP is used in the manufacture of pyrotechnics, semiconductors, fertilizers, incendiary shells, smoke bombs (in combination with butyl rubber), and tracer bullets. It is also used in organic synthesis reactions and in the manufacture of phosphoric acid, phosphine, phosphoric anhydride, phosphorus pentachloride, phosphorus trichloride, and in electroluminescent coatings. RP (2-10%) is also used as a flame-retardant additive for plastics such as polyamides. 

Less than 10% of the polyamide produced is made in a flame retardant version. The best system is composed of a combination of red phosphorus and zinc borate (see table above). The only drawback of this system is its color which is restricted to brick red or black. If other colors are required, ammonium polyphosphate is used either in combination with organic flame retardants or with antimony trioxide. It is possible to manufacture a very wide range of colors in the halogen free system. Some systems make use of the addition of novolac or melamine resins. For intumescent applications, ammonium polyphosphate, in combination with other components, is the most frequently used additive. Figure 13.6 shows that fillers such as calcium carbonate and talc (at certain range of concentrations) improve the effectiveness of ammonium polyphosphate. This is both unusual and important. It is unusual because, in most polymers, the addition of fillers has an opposite influence on the efficiency of ammonium polyphosphate and it is important because ammonium polyphosphate must be used in large concentrations (minimum 20%, typical 30%) in order to perform as a flame retardant. 

For quality control reasons, rapid screening methods are needed to identify the volatiles in polymeric materials collected for recycling. HS-SPME-GC-MS was shown to be a fast and sensitive method to screen for brominated flame retardants in recycled polyamide materials [78]. HS-SPME effectively extracted several brominated compounds, all possible degradation products from the common flame-retardant Tetrabromobisphenol A from recycled polyamide 6.6. Furthermore, the high extraction capacity of the PDMS/DVB stationary phase towards aromatic compounds was demonstrated, as the HS-SPME-GC-MS method allowed the extraction and iden-tiflcation of brominated benzenes, from a complex matrix only containing trace amounts of analytes. In addition, degradation products from an antioxidant, a hindered phenol, were extracted. Figure 14 shows a typical chro-... 

Some three decades ago, scientists from the Du Pont company developed polycondensation methods which allowed the preparation of high molecular weight wholly aromatic polyamides. The first commercially produced wholly aromatic polyamide fibre was poly(m-phenyleneisophthalamide) (Nomex, Du Pont, 1967) [la, c]. Some years later, development of the preparation and processing of poly(p-phenyleneterephthalamide) (PPTA) led to the commercialization of the para product Kevlar (Du Pont) in the early seventies [lb, c]. While Nomex shows excellent thermal stability and flame-retardance, and indeed is referred to as a heat and flame resistant aramid fibre, Kevlar fibre also has similar properties, but in addition it has exceptional tensile strength and modulus, and is referred to as an ultra-high strength, high modulus aramid fibre. 

Polyamides, such as PA 6, PA 12 or PA 6.6, PET and PEN, can be made flame retardant by the addition of a mixture of melamine cyanurate and an organo poly(phosphonate). The poly(phosphonate) acts in addition as a plasricizer, improving the mechanical properries of the polymer and assisting the dispersion of the melamine cyanurate. 

As stated above, conventional synthetic fibres may be rendered inherently flame retardant during production by either incorporation of a flame retardant additive in the polymer melt or solution prior to extrusion or by copolymeric modification before, during, or immediately after processing into filaments or staple fibres. Major problems of compatibility, especially at the high tanperatures used to extrude melt-extruded fibres like polyamide, polyester, and polypropylene and in reactive polymer solutions such as viscose dope and acrylic solutions, have ensured that only a few such fibres are commercially available. A major problem in developing successful inherently flame retardant fibres based on conventional fibre chemistries is that any modification, if present at a concentration much above 10wt% (whether as additive or comonomer), may seriously reduce tensile properties as well as the other desirable textile properties of dyeability, lustre and appearance, and handle, to mention but a few. 

The general paucity of FR polyamides reflects their high melt reactivities and hence poor potential flame retardant additive compatibilities. The only additive currently marketed as a potential flame retardant for polyamide fibres is Clarianf s Exolit OP930/935, which is based on a fine particulate (Dj(, 2-3pm), aluminium diethyl phosphinate. This phosphinate may be used alone or combined with melamine polyphosphate, although in bulk polymers total levels of 15wt% or so are required for acceptable levels of flame retardancy. To date it is not known whether commercially successful PA6 and PA6.6 fibres based on this agent are available. 

Uses Flame-retardant additive for polymeric systems (thermoplastics, thermosets, elastomers), esp. polyamides and polyolefins for wire and cable applies. inert filler in grinding wheels Manuf./Disthb. Occidental http //WWW. oxychem. com Trade Name Synonyms Dechlorane Plus 25 [Occidental http //www.oxychem.com]-, Dechlorane Plus 35 [Occidental http //www.oxychem.com], Dechlorane Plus 515 [Occidental http //www.oxychem.com], Wyfire Y-H-64 [Rhein Chemie http //WWW. rheinchemie. com]... 

Melamines and their derivatives are the outcomes of recent developments directed at finding non-halogenic flame-retardants. They are primarily recommended for polyamides and polyolefins. This group of additives is not yet commonly available. 

In addition to flame-retardancy, zinc borates have a smoke suppressing effect. When used in polyamides, they counteract the reduction in the tracking index (cf. Section 3.2.2.1) caused by the halogenic flame-retardants. ... 

Polyamides are less combustible plastics due to their chemical composition. Unfilled and unmodified PA 6 and PA 66 are rated V-2 according to UL 94, with an oxygen index of about 25 per cent without any added agents. One peculiarity is that glass fibres, mineral fillers, and some additives (such as the impact modifiers) actually enhance the flammability of polyamides they are rated only HB when not flame-retarded. A drawback of polyamides is dripping during the combustion. 

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