りん酸トリフェニル

外観

白色のフレーク

定義

本品は、リン酸(*)とフェノール(*)とのトリエステルであり、次の化学式で表される。
参照表示名称：リン酸, フェノール

溶解性

エタノール及びアセトンに溶けやすく、水にほとんど溶けない。

解説

リン酸トリフェニル,融点49～50 ℃，沸点245 ℃(1.5 kPa)．d²⁵₀ 1.185．n²⁵_D 1.563．不燃性で，水に不溶，ベンゼン，エーテル，クロロホルム，アセトンに易溶．可塑剤，高分子用難燃剤などに用いられる．LD50 3800 mg/kg(ラット，経口)．

森北出版「化学辞典（第2版）

用途

プラスチック可塑剤。

用途

セルロースアセテートフィルムに対して難燃性、透明性、耐水性、柔軟性及び非粘着性を付与する可塑剤。フェノール樹脂積層板の難燃性可塑剤、エンジニアリングプラスチックスの難燃剤兼可塑剤。合成ゴムに添加して柔軟性、耐ガソリン性、耐鉱油性を付与する。その他塗料の難燃剤、ニトロセルロースフィルムの引張り強度付与など

製造

リン酸トリフェニル,フェノールと塩化ホスホリルを無溶媒で加熱し，発生する塩化水素を除去したのち，減圧蒸留すると得られる．

化粧品の成分用途

可塑剤

化学的特性

Triphenyl phosphate (TPP) is a colorless crystalline powder with a faint, phenol-like odor. Triphenyl phosphate is practically insoluble in water at 1.9 × 10 7 mg/l at 24 °C (Yalkowsky et al., 2010). It is very soluble in carbon tetrachloride (Haynes, 2010) and is soluble in most lacquers, solvents, thinners, and oils, as well as in alcohol, benzene, ether, chloroform, and acetone (Lewis, 1996). It begins to decompose at about 600 °C in inert gas, and in a large excess of air, complete combustion to carbon dioxide occurs in the range 800–900 °C (Lhomme et al., 1984). Hydrolysis of TPP occurs very slowly in acidic or neutral solutions, but occurs rapidly in alkaline solutions (Barnard et al., 1966).

使用

Triphenyl phosphate is known as a product with manifold fields of applications regarding its qualities in particular as a flame retardant. One primary use is as a flame retardant in phenolic- and phenylene oxide-based resins for the manufacture of electrical and automobile components, for auto upholstery, and as a nonflammable plasticizer in cellulose acetate for photographic films. It has also been used to impregnate roofing paper. Triphenyl phosphate occurs as a plasticizer in various lacquers and varnishes (O'Neil, 2006), and as a component of lubricating oil and hydraulic fluids (ACGIH, 2012).

定義

ChEBI: Triphenyl phosphate is an aryl phosphate resulting from the formal condensation of phosphoric acid with 3 mol eq. of phenol. It has a role as a flame retardant and a plasticiser. It is functionally related to a phenol.

主な応用

Triphenyl Phosphate is used in the insecticidal composition. It is also use in hydraulic liquids, and adhesives, inks, coatings, as a plasticizer in lacquers and varnishes, and as a substitute for camphor in celluloid materials to make the latter stable and fireproof.

製造方法

Triphenyl phosphate is prepared by reacting phosphorus pentoxide and phenol (Budavari, 2001), or by reacting phosphorus oxychloride and phenol (Snyder, 1990). On a larger scale phosphorus oxychloride and phenol are reacted in an esterification tank with heating. The HCL formed is trapped and condensed, while the crude triphenyl phosphate runs into a large tank where it is purified.

反応プロフィール

Organophosphates, such as Triphenyl phosphate, are susceptible to formation of highly toxic and flammable phosphine gas in the presence of strong reducing agents such as hydrides. Partial oxidation by oxidizing agents may result in the release of toxic phosphorus oxides.

危険性

Toxic by inhalation. Cholinesterase inhibitor. Questionable carcinogen.

健康への影響

Non-industrial:
An allergic reaction in a 67-year old woman to spectacle frames containing triphenyl phosphate was reported. Patch tests with analytical grade triphenyl phosphate in that individual indicated a reaction at concentrations as low as 0.05%. This observation was confirmed in another male patient (Carlsen et al 1986).
Industrial:
Occupational exposure of men engaged in manufacturing triphenyl phosphate produced a statistically significant reduction in erythrocyte acetylcholinesterase activity and plasma cholinesterase activity. There was no evidence of adverse clinical effects in men exposed to triphenyl phosphate for as long as 10 years. Exposure was to triphenyl phosphate mist, vapor, and dust at a weighted average air concentration of 3.5 mg/m3 (Sutton et al 1960).

火災危険

Noncombustible solid. Incompatibility— none.

安全性プロファイル

Poison by subcutaneous route. Moderately toxic by ingestion. Absorbed slowly, particularly by skin contact. Not a potent cholinesterase inhibitor. Combustible when exposed to heat or flame. To fight fire, use CO2, dry chemical. When heated to decomposition it emits toxic fumes of POx. See also TRITOLYL PHOSPHATE.

職業ばく露

Triphenyl phosphate is used to impregnate roofing paper and as a fire-resistant plasticizer in plastics; for cellulose esters in lacquers and varnishes. Used in making adhesives, gasoline additives; flotation agents; insecticides, surfactants, antioxidants, and stabilizers. A substitute for camphor.

環境運命予測

Chemical/Physical. When an aqueous solution containing triphenyl phosphate (0.1 mg/L) and chlorine (3 to 1,000 mg/L) was stirred in the dark at 20 °C for 24 h, the benzene ring was substituted with one to three chlorine atoms (Ishikawa and Baba, 1988). The reported hydrolysis half-lives at pH values of 8.2 and 9.5 were 7.5 and 1.3 d, respectively (Howard and Doe, 1979).
Decomposes at temperatures greater than 410 °C (Dobry and Keller, 1957)

代謝

Rat liver microsomal enzymes degraded triphenyl phosphate in the presence of NADPH, but also in the absence of NADPH. The product of incubation was diphenyl phosphate. It was clear that the reaction was cytochrome P-450-linked since the reaction was inhibited by carbon monoxide (Sasaki et al 1984). Goldfish liver microsomes metabolized only about 10% of triphenyl phosphate (Sasaki et al 1985). Houseflies treated with triphenyl phosphate were analyzed after 24 h and the presence of diphenyl p-hydroxyphenyl phosphate was confirmed (Eto et al 1975).

輸送方法

UN3077 Environmentally hazardous substances, solid, n.o.s., Hazard class: 9; Labels: 9-Miscellaneous hazardous material, Technical Name Required.

純化方法

Crystallise the phosphate from EtOH or pet ether (b 60-80o)/EtOH. [Cox & Westheimer J Am Chem Soc 80 5441 1958, Krishnakumar & Sharma Synthesis 558 1983, Cherbuliez in Organo Phosphorus Compounds (Kosolapoff & Maier eds) Wiley Vol 6 pp 211-577 1973, Beilstein 6 III 658, 6 IV 720.]

Toxicity evaluation

Triphenyl phosphate(TPP) is neurotoxic, causing paralysis at high dosages. Like tri-o-cresyl phosphate (TOCP), it is a cholinesterase inhibitor. The acute oral toxicity is low. The acute toxicity via subcutaneous administration is low to moderate. The toxic symptoms from high dosages in test animals were tremor, diarrhea, muscle weakness, and paralysis.
LD50 value, oral (mice): 1320 mg/kg
LD50 value, subcutaneous (cats): 100 mg/kg
Cleveland et al. (1986) investigated the acute and chronic toxicity to various species of freshwater fish of phosphate ester compounds containing TPP. The adverse toxic effects occurred at exposure concentrations of 0.38–1.0 mg/L.

不和合性

Incompatible with strong oxidizers; strong acids; nitrates may cause fire or explosions. Phosphates are incompatible with antimony pentachloride, magnesium, silver nitrate, zinc acetate.

廃棄物の処理

Incinerate in furnace equipped with alkaline scrubber.