Phenolics, flame retardants

Thomsen, C., Janak, K., Lundanes, E., and Becher, G., Determination of phenolic flame retardants in human plasma using solid phase extraction and gas chromatography-electron capture mass spectrometry, J. Chromatogr. B, 750, 1-11, 2001. 

Resin Phenolic Flame-retardant properties/available in prepreg format/requires temperature cure... 

Brominated Phenols. Tribromophenol [75-80-9] and dibromophenol [615-58-7] are both prepared through bromination of phenol. These are not actually used as reactive flame retardants, but rather as starting materials for other flame retardants such as BTBPE [37853-59-1] and epoxy oligomers. 

The phosphonate esters, HP(=0(OR)2, of alkylated phenols are used extensively as lubricating-oil additives to control bearing corrosion and oxidation, and to impart antimst properties as stabilizers, as antioxidants (qv) and flame retardants in plastics, as specialty solvents, and as intermediates (see Corrosion AND corrosion control Heat stabilizers). 

To enhance flame retardancy without use of additives, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane (tetrabromobis-phenol A) has been used in copolymers with bis-phenol A. 

Phenol, formaldehyde, and urea have been copolymerized to achieve resins and subsequent networks with improved flame retardance and lower cost relative to phenol-formaldehyde analogues. The condensation of a phenolic methylol group with urea (Fig. 7.32) is believed to be the primary reaction under the weakly acidic conditions normally used. 

TABLE 7.10 Flame Retardance of Networks Prepared from Phenolic Novolac Crosslinked with Various Epoxies... 

Benzoxazines are heterocyclic compounds obtained from reaction of phenols, primary amines, and formaldehyde.98,99 As described previously, they are key reaction intermediates in the HMTA-novolac cure reaction.40,43 Crosslinking benzoxazine monomers at high temperatures gives rise to void-free networks with high Tgs, excellent heat resistance, good flame retardance, and low smoke toxicity.100 As in HMTA-cured novolac networks, further structural rearrangement may occur at higher temperatures. 

Phenolic networks, 411 Phenolic-novolac-cured systems, 415 Phenolic novolac-epoxy networks, flame retardance of, 415 Phenolic oligomers, 375... 

Recently, several reports of the flame-retardant properties of boron-containing bisphenol-A resins have appeared from Gao and Liu.89 The synthesis of a boron-containing bisphenol-A formaldehyde resin (64 and 65) (Fig. 42) from a mixture of bisphenol-A, formaldehyde, and boric acid, in the mole ratio 1 2.4 0.5, has been reported.893 The kinetics of the thermal degradation and thermal stability of the resins were determined by thermal analysis. The analysis revealed that the resin had higher heat resistance and oxidative resistance than most common phenol-formaldehyde resins. 

One of the present authors (31) has developed a series of additives which combine the features of both free radical inhibitors and flame retardants of the tetrabromophthalimide or chlorendic imide type with hindered phenol antioxidant structures such as the following compounds ... 

We have recently evaluated the chlorendic imide/hindered phenol for its effect on the oxygen index of polyethylene, and we found only a miniscule increase, not considred statistically significant, in comparison to the same loading of chlorine as chlorendic anhydride. We believe that if the antioxidant approach to flame retardancy is to be successful, special high temperature antioxidant structures must be designed for this purpose. 

Oligomeric flame retardants, 11 470-474 Oligomeric peroxides, 18 480 Oligomeric phenolic poly-(mainly tetra-)sulfides, 23 644... 

Among the chemicals which have been shown to be mutagens in Salmonella (as well as other short-term tests) that have recently been shown to be carcinogens are 1,2-dichloroethane (10 x 109 Ibs/year, U.S.), tris-dibromopropyl phosphate (the flame retardant used in children s polyester sleepwear), sulfallate (a pesticide), o-phenylene-diamine, 2,4-diaminoanisole (hair dye ingredient), 2-nitro-p-phenylenediamine (hair dye ingredient), and 4-amino-2-nitro-phenol (hair dye ingredient). 

Optical properties are related to both the degree of crystallinity and the actual polymer structure. Most polymers are transparent and colorless, but some, such as phenolic resins and polacetylenes, are colored, translucent, or opaque. Polymers that are transparent to visible light may be colored by the addition of colorants, and some become opaque as the result of the presence of additives, such as fillers, stabilizers, flame retardants, moisture, and gases. 

Eriksson P, Jakobsson E, Fredriksson A. 1998. Developmental neurotoxicity of brominated flame-retardants, polybrominated diphenyl ethers, and tetrabromo-bis-phenol A. Organohalogen Compounds 35 375-377. 

Flame retardants are preferably added for wires, such as high-voltage power cables through with a large quantity of current flows. Antioxidants include phenolic antioxidants, phosphorus antioxidants and sulfur antioxidants. 

Suitable fire retardant materials include halogen compounds in combination with antimony compounds, including, tetrabromobis-phenol A and antimony trioxide. Examples for halogen free flame retardants are phosphate esters, such as Hoechst Celanese AP422 or Hoechst Celanese IFR 23. 

Polychlorinated Dibenzo-(p)-Dioxins and Dibenzo-Furans. Another group of compounds that we need to specifically address are the polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzo-furans (PCDFs) (Fig. 2.15). The PCDDs and PCDFs are not intentionally produced but are released into the environment from various combustion processes and as a result of their occurrence as unwanted byproducts in various chlorinated chemical formulations (e.g., chlorinated phenols, chlorinated phenoxy herbicides see Alcock and Jones, 1996). Because some of the PCDD and PCDF congeners are very toxic (e.g., 2,3,7,8-tetrachloro dibenzo-p-dioxin, see margin), there have been and still are considerable efforts to assess their sources, distribution, and fate in the environment. Similarly to the PCBs or DDT (see above), the PCDDs and PCDFs are highly hydrophobic and very persistent in the environment. It is therefore not surprising that they have also been detected everywhere on earth (Brzuzy and Hites, 1996 Lohmann and Jones, 1998 Vallack et al., 1998). Finally, we should note that polybrominated diphenylethers (PBDEs, see margin) that, like the PBBs (see above), are used as flame retardants, are of increasing environmental concern (de Boer et al., 2000). 

The newer open-cell foams, based on polyimides (qv), polybenzimidazoles, polypyrones, polyureas, polyphenylquinoxalines, and phenolic resins (qv), produce less smoke, are more fire resistant and can be used at higher temperatures. These materials are more expensive and used only for special applications including aircraft and marine vessels. Rigid poly (vinyl chloride) (PVC) foams are available in small quantities mainly for use in composite panels and piping applications (see Flame retardants Hrat-rrststantpot.ymf.rs). 

Incubation in soils showed that polybrominated biphenyls were resistant to degradation, but were apparently not taken up by plants or leached into groundwater [261]. Commercial formulations of brominated aromatic flame retardants had variable composition some contained highly brominated phenols, but no evidence of contamination with dibenzodioxins and dibenzofurans was found [198]. 

TG-MS is an ideal technique for identifying residual volatiles in polymers. The detection of residual volatiles (and of other impurities) can often yield clues as to manufacturing processes. In many cases, such as in the determination of highly volatile materials, of residual solvents or plasticisers, use of TG-MS is requested. Specifically, there are reports on the entrapment of curing volatiles in bismaleimide laminates [145] and elastomers [48], on the detection of a curing agent (dicumylperoxide) in EPDM rubbers and of bromine flame retardants in electronic waste [50], of plasticisers such as bambuterol hydrochloride [142] or TPP and diethylterephthalate in cellulose acetate [143], on solvent extraction and formaldehyde loss in phenolic resins [164], and on the evolution of toxic compounds from PVC and polyurethane foams [146]. 

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