Polyethylene terephthalate flame-retardant

Convincing evidence for phosphorus/bromine synergy has now been found in a 2/1 polycarbonate/polyethylene terephthalate blend. Phosphorus and bromine blends were studied as well as compounds which have both elements in the same compound. The relative flame retardant efficiencies of phosphorus and bromine are also reported. 

A 2/1 blend of polycarbonate and polyethylene terephthalate (PC/PET) was flame retarded with bromine, phosphorus, a blend of bromine and phosphorus, and compounds containing both phosphorus and bromine in the same molecule. All compositions contained 0.5 % Teflon 6C as a drip inhibitor and where specified 5 % of an impact modifier. 

We previously reported that brominated aromatic phosphate esters are highly effective flame retardants for polymers containing oxygen such as polycarbonates and polyesters (9). Data were reported for use of this phosphate ester in polycarbonates, polyesters and blends. In some polymer systems, antimony oxide or sodium antimonate could be deleted. This paper is a continuation of that work and expands into polycarbonate alloys with polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and acrylonitrile-butadiene-styrene (ABS). 

Aromatic polyphosphonates have been found to be especially effective flame retardant additives for polyester compositions (j), 1, 8), especially for polyethylene terephthalate. 

PBDEs are used in different resins, polymers, and substrates at levels ranging from 5 to 30% by weight (EU 2001). Plastic materials that utilize PBDEs as flame retardants include ABS polyacrylonitrile (PAN) polyamide(PA) polybutylene terephthalate (PBT) polyethylene (PE) cross-linked polyethylene (XPE) polyethylene terephthalate (PET) polypropylene (PP) polystyrene (PS) high-impact polystyrene (HIPS) polyvinyl chloride (PVC) polyurethane (PUR) and unsaturated polyester (UPE). These polymers and examples of their final products are summarized inTable 5-2 (Hardy 2002 WHO 1994a). 

Condensation monomers having the benzimidazolin-2-one ring system have found utility as modifiers in polyester synthesis. In particular, halogenated diols (73) and dicarboxylic acids (74) may be incorporated (78MI11100) into polyethylene terephthalate) or poly(butyl-ene terephthalate) at fairly low levels to impart flame retardancy. This can be accomplished without adverse effects upon other polymer properties. 

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... 

Whereas UL 94 delivers only a classification based on a pass-and-fail system, LOI can be used to rank and compare the flammability behavior of different materials. In Figure 15.2 the increasing LOI values are presented for different polymers as an example POM = poly(oxymethylene), PEO = poly(ethyl oxide), PMMA = poly(methyl methacrylate), PE = polyethylene), PP, ABS, PS, PET = polyethylene terephthalate), PVA = poly(vinyl alcohol), PBT, PA = poly(amide), PC, PPO = poly(phenylene oxide), PSU, PEEK = poly(ether ether ketone), PAEK = poly(aryl ether ketone), PES, PBI = poly(benzimidazole), PEI = poly(ether imide), PVC = poly(vinyl chloride), PBO = poly(aryl ether benzoxazole), PTFE. The higher the LOI, the better is the intrinsic flame retardancy. Apart from rigid PVC, nearly all commodity and technical polymers are flammable. Only a few high-performance polymers are self-extinguishing. Table 15.1 shows an example of how the LOI is used in the development of flame-retarded materials. The flame retardant red phosphorus (Pred) increases... 

M. Day and D. M. Wiles, Influence of temperatnre and environment on the thermal decomposition of polyethylene terephthalate fibres, with and withont the flame retardant tri(2,3)-dibromopropyl phosphate., J. Anal Appl J rolysis, 7, 65-82, (1984). 

The most important commercial blends of BPA-PC are poly(acrylonitrile-butadiene-styrene) (PC/ABS) and polybutylene terephthalate (PC/PBT) or polyethylene terephthalate (PET). Commercial grades of PC/ABS include CYCOLOY (GE), Bayblend (Bayer), and PULSE (Dow). PC/ABS blends exhibit improved flow and processability and enhanced low-temperature impact strength in comparison to PC (Fig. 3). These blends are widely used in applications requiring enhanced impact resistance, such as interior automotive parts and computer and electronics applications such as computer housings and cell phones. Non-halogenated flame-retardant PC/ABS blends are widely available. Poly(acrylic-styrene-acrylonitrile) (PC/ ASA) blends (GELOY , GE Luran , BASF) provide improved weatherability for outdoor applications such as exterior automotive parts, but exhibit reduced impact performance at low temperatures in comparison to PC/ABS. PC/PBT or PET blends (XENOY , GE Makroblend , Bayer) provide enhanced chemical resistance and weatherability for applications such as lawn and garden equipment and automotive bumpers and fasdas. 

However, one of our customers (27) found it to be an effective additive to polyethylene terephthalate in order to increase the strength and reduce the striation when the polymer was extruded into polyester film. This certainly was an unexpected commercial success. I would regard this commercial success as pure luck on our part. After all. Dr. Walsh s group designed the compound to be a flame retardant. 

Fire retardants used in polystyrene (PS) include montmorillonite clay, polytetrafluoro-ethylene (PTFE) [8], bromine-based flame retardants such as brominated bisphenol A [9], brominated phenyl oxide or tetrabromophthalic anhydride, or magnesium hydroxide [10,11]. Sanchez-Olivares and co-workers [12], in their study of the effect of montmorillonite clay on the burning rate of PS and PS-polyethylene terephthalate blends, showed that increased combustion rate accompanied the incorporation of montmorillonite particles in high-impact polystyrene (FlIPS) formulations. 

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. 

PDBS-80 was the first in the series. This material is a homopolymer of dibromostyrene that contains 59-60% bromine. Its primary applications are in high-temperature polyamides and polyethylene terephthalate (PET) because it has excellent flow characteristics and very good thermal stability. In addition, there are benefits of excellent colour retention. The main weakness of this approach is the bromine content relative to the competitive material. Today s competition contains around 68% bromine. This can translate into a 2-3 parts difference in the load level needed in the protected polymer to give equivalent flame retardancy. 

AMGARD 1045 can advantageously be added to polyethylene terephthalate melt before spinning. These products are also useful flame retardants for other thermoplastics, thermoset polyester resins, polyurethanes, polycarbonates, nylon 6, and textile backcoating. 

Hydroxymethyl)phenylphosphinic acid (an adduct of formaldehyde and phenylphosphinic acid) can he thermally dehydrated to form oligomers which are useful in flame retarding polyethylene terephthalate (60). These may have reached commercial usage in Europe. 

Within the technologies of polyethylene terephthalate production, this chapter focuses on nonpolymer modifications. That means, that speciality products based on bicomponent systems (combinations with different polymers), and polymer additives (for anti-pilling, antistatic, flame-retardant, antibacterial and heat resistance properties) are not specifically described. 

Until 2003, Chen s [28], Qu s [29-31], and Hu s [32] groups independently reported nanocomposites with polymeric matrices for the first time the. In Hsueh and Chen s work, exfoUated polyimide/LDH was prepared by in situ polymerization of a mixture of aminobenzoate-modified Mg-Al LDH and polyamic acid (polyimide precursor) in N,N-dimethylactamide [28]. In other work, Chen and Qu successfully synthesized exfoliated polyethylene-g-maleic anhydride (PE-g-MA)/LDH nanocomposites by refluxing in a nonpolar xylene solution of PE-g-MA [29,30]. Then, Li et al. prepared polyfmethyl methacrylate) (PMMA)/MgAl LDH by exfoliation/adsorption with acetone as cosolvent [32]. Since then, polymer/LDH nanocomposites have attracted extensive interest. The wide variety of polymers used for nanocomposite preparation include polyethylene (PE) [29, 30, 33 9], polystyrene (PS) [48, 50-58], poly(propylene carbonate) [59], poly(3-hydroxybutyrate) [60-62], poly(vinyl chloride) [63], syndiotactic polystyrene [64], polyurethane [65], poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] [66], polypropylene (PP) [48, 67-70], nylon 6 [9,71,72], ethylene vinyl acetate copolymer (EVA) [73-77], poly(L-lactide) [78], poly(ethylene terephthalate) [79, 80], poly(caprolactone) [81], poly(p-dioxanone) [82], poly(vinyl alcohol) [83], PMMA [32,47, 48, 57, 84-93], poly(2-hydroxyethyl methacrylate) [94], poly(styrene-co-methyl methacrylate) [95], polyimide [28], and epoxy [96-98]. These nanocomposites often exhibit enhanced mechanical, thermal, optical, and electrical properties and flame retardancy. Among them, the thermal properties and flame retardancy are the most interesting and will be discussed in the following sections. 

The largest volume flame retardant is alumina trihydrate, AI2O3 3H2O. In the flame, water is released and this cools the plastic, preventing further combustion. Alumina trihydrate is used in polymers such as polyolefins, PVC, polyacrylates, and thermoset polyesters. It cannot be used in polymers such as polycarbonate, nylon 6,6, or polyethylene terephthalate because these are processed at temperatures that will cause the evolution of water during processing. 

Bhaskar T, Mitan NM, Onwudili J, Muto A, Williams P, Sakata Y (2010) Effect of polyethylene terephthalate (PET) on the pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br). J Mater Cycles Waste Manage 10(4) 332-340... 

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