Triphenyl, cellulosics

Triphenyl phosphate [115-86-6] C gH O P, is a colorless soHd, mp 48—49°C, usually produced in the form of flakes or shipped in heated vessels as a hquid. An early appHcation was as a flame retardant for cellulose acetate safety film. It is also used in cellulose nitrate, various coatings, triacetate film and sheet, and rigid urethane foam. It has been used as a flame-retardant additive for engineering thermoplastics such as polyphenylene oxide—high impact polystyrene and ABS—polycarbonate blends. 

Although many plasticisers have been suggested for cellulose acetate very few have been used in practice. The most important of these are dimethyl phthalate (8 = 21.4), triacetin (8 = 20.3) and triphenyl phosphate (8 = 20.0), each of which have a solubility parameter within one unit of that of cellulose diacetate (-22.0). (All in units ofMPa. )... 

Triphenyl phosphate is a crystalline solid which has less compatibility with the polymer. This may be expected from solubility parameter data. It is often used in conjunction with dimethyl phthalate and has the added virtues of imparting flame resistance and improved water resistance. It is more permanent than DMP. Triacetin is less important now than at one time since, although it is compatible, it is also highly volatile and lowers the water resistance of the compound. Today it is essential to prepare low-cost compounds to allow cellulose acetate to compete with the synthetic polymers, and plasticisers such as ethyl phthalyl ethyl glycollate, which are superior in some respects, are now rarely used. 

The primary OH group can be selectively blocked by the bulky triphenyl-methyl (trityl) moiety, followed by esterification at the secondary OH groups and removal of the protecting trityl group. Thus 2,3-di-O-acetyl cellulose has been obtained by this procedure. Moreover, regioselectively substituted mixed cellulose esters, acetate/propionate, were prepared by subsequent acy-... 

Phosphites. The phosphates, second only to phthalates in production volume, are favored for flame resistance and low volatility. Tricresyl phosphate (mixed meta and para isomers) is the most popular it is used in polyvinyl chloride and in nitrocellulose lacquers. Resins plasticized with tricresyl phosphate are deficient in low-temperature flexibility. Diphenyl cresyl phosphate and triphenyl phosphate are other examples, the former for polyvinyl chloride, the latter for cellulose acetate. Diphenyl-2-ethylhexylphosphate is preferred to tricresyl phosphate in polyvinyl chloride where its low toxicity and improved low-temperature flexibility are required. Tn(2-elliylliexyl)-phosphale is outstanding among phosphates used in polyvinyl chloride with respect to low-temperature flexibility in flame- and oil resistance, however, it is inferior to tricresyl phosphate. Tri(butoxvethyl)phosphate finds some use in synthetic rubber. 

Minor industrial uses include the application of silver iodide as a smoke for the seeding of clouds to induce rainfall. Compounds used for obtaining some nonflammable plastics and cellulose are benzyltriphenyl-phosphoniumiodides and [2,-(acetyloxy)ethyl] triphenyl-phosphoniumiodides (see Flame RETARDANTS, HALOGENATED FLAME retardants) (142). The addition of iodine to an aromatic hydrocarbon such as -butylbenzene results in the formation of charge-transfer complexes that display outstanding effectiveness as lubricants for hard-to-lubricate metals (143), such as titanium or steels (see also LUBRICATION AND LUBRICANTS). Iodine is also used in the production of high purity metals such as titanium, silicon, hafnium, and zirconium (144). 

An obvious limitation of the application of a-cyclodextrin for a wider variety of compounds is its narrow cavity diameter. Larger molecules do not fit the cavity. Due to its low aqueous solubility, 6-cyclodextrin is not adequate for similar purposes. However its highly soluble polymer (a low molecular crosslinked product) proved to be very useful for the TCL separation of larger molecules. The wider cavity diameter, and probably some cooperativeness between the vicinally fixed cyclodextrin-moieties, render such soluble polymers adequate in the mobile phase for a great variety of compounds. The reversed phase TLC-behaviour of antibiotics polymixine (48), 17 substituted s-triazine derivatives (49), 25 triphenyl-methane derivatives and analogues (50) 33 nitrostyrene derivatives (51) and 21 barbiturates (52) were studied on silica or cellulose plates. 

A relatively novel class of derivatives is obtained by the covalent incorporation of organometallic moieties into cellulose. For example, cellulose ferro-cenyl derivatives have been prepared by esterification of cellulose with an intermediate derived from ferrocene carboxylic acid and triphenyl phosphite in the presence of pyridine [84]. An enzymatically cleavable cellulose ester has been developed [85], and prodrugs have been coupled to the hydroxyl or carboxyl functions of C-terminal aromatic amino acids of cellulose peptide derivatives for controlled release applications [86]. 

The reactivity of cellulose toward tri(p-toluenesulfonyl)methane chloride was recently examined [89]. The tosyl reagent is more reactive than trityl chloride, and the primary hydroxyl position exhibited 43 times more reactivity than the secondary hydroxyl groups. The products were used as intermediates in the synthesis of selectively modified cellulose derivatives [89]. As mentioned earlier, a high DS, organosol trimethylsilylcellulose has been prepared in DMAc/LiCl [10]. The condensation of polysaccharides with triphenyl-methyl (trityl) chloride proceeds generally with preference for the primary hydroxyl positions. The tritylation of cellulose occurs initially 58 times faster at the hydroxyl group at C6 than at either C2 or C3 [90]. 

Cellulose can be modified with organostannane chlorides, such as dibutyl or triphenyl derivatives [91,92], or with organotin halides in the presence of bisethylenediamine copper(II) hydroxide [93]. Epoxy-activated cellulose was prepared by reacting cellulose acetate fibers with sodium methoxide, followed by reacting it with epichlorohydrin in DMSO. This epoxy-activated cellulose has proved to be a useful intermediate to react with substances containing active hydrogen, such as amine, amino acid, or carboxylic acids [94], as shown in Fig. 3. Epoxidized cellulose has also been converted to a thiol derivative via reduction of a thiosulfate intermediate [95], and sulfoethylcellu-[ose has been obtained from sodium chloroethanesulfonate [96]. Cellulose... 

Separations of [njhelicene racemates have also been attempted using n-acids, such as 2-(2,4,5,7)-tetranitrofluorenylidene-9-aminooxypropionic acid (TAPA, 112, see above) its butyric acid analogue TAB A 113 and binaphthyl-2,2-diyl-hydrogenphosphate (BPA, 115 Other employed methods were inclusion chromatography on triacetyl cellulose or helical polymers like (-l-)-poly(triphenyl-methyl-methacrylate [(-l-)-PTrMA, 776]... 

Azzolina, O., Collina, S., Ghislandi,V., Optical resolution of aryloxypropionic acids and their esters by HPLC on cellulose tris-3,5-dimethyl-triphenyl carbamate... 

Shrinkage, tackiness and increased brittleness due to the migration and subsequent evaporation of plasticiser from between the cellulose acetate chains, is also a frequent cause of degradation. The degradation of some plasticisers has been shown to increase acidity of cellulose acetate-containing materials. Triphenyl phosphate, used as a plasticiser for cellulose acetate since the 1940s, decomposes to form diphenyl phosphate and phenol. Diphenyl phosphate is a strong acid so it is likely to accelerate the deacetylation of cellulose acetate. 

In 1910, the Celluloid Company patented use of triphenyl phosphate in combination with cellulose acetate to circumvent the inherent flammability danger of cellulose nitrate (5). Since then, use of phosphate plasticizers to reduce flammability of polymer compounds has become widespread. Other plasticizer types have become standards for their effect on other specific properties. 

The majority of investigations on the degradation of cellulose acetate have been conducted on photographic film (cellulose triacetate) rather than moulded material. like cellulose nitrate, cellulose acetate (CA) is deteriorated by both physical and chemical factors and the physical cause of degradation is plasticizer loss. Three-dimensional objects moulded from cellulose acetate comprise 20-40 per cent by weight plasticizer. Typical plasticizers include triphenyl... 

The low-volatility, flame-resistant phosphoric acid esters have maintained their position in products subjected to high levels of mechanical strain such as conveyor belts. Triphenyl phosphate, used only for molding compounds made of cellulose esters, is a practically noncombustible product that is not soluble in benzine. Tricresyl phosphate (TCP) is a flame-retardant plasticizer for PVC products subjected to heavy mechanical stress. The esters of the aliphatic dicarboxylic acids (adipic, azelaic, and sebacic acid) are used as plasticizers for PVC and PVAC. These products are resistant to cold and light. The esters of higher fatty acids such as pelargonates, laurates, palmitates, stearates, and ricinoleates are, strictly speaking, not plasticizers, but are rather used as extenders, secondary plasticizers, or lubricants. 

Chem. Descrip. Triphenyl phosphate CAS 115-86-6 EINECS/ELINCS 204-112-2 Uses Rame retardant platinizing agent, plastidzer tor collodion cotton plastidzer w/o gelatinizing properties for acetyl cellulose reduces tiamm. ot NC and acetyl cellulose-based plastic compds. and lacquer films flame retardant plasticizer tor photographic film materials, surf, coatings, phenolic laminates, cellulose acetate film/compds., rubber articles made from acrylonitrile-butadiene, polychloroprene rubber Features Not compat. with PVC... 

Chem. Descrip. Triphenyl phosphate CAS 115-86-6 EINECS/ELINCS 204-112-2 Uses Flame retardant, plasticizer for photographic safety film, sheets, cast triacetate film (primary plasticizer), molded acetate prods., nitrocellulose, ethyl cellulose, and cellulose acetate butyrate coatings, ABS, unsat. polyester, PVAc, PVC, flexible PU foam Features Mostly used combined with other plasticizers improves dimensional stability and dielec. str. 

Some triesters increase flame resistance and dye-ability when incorporated into organic polymers (Section 12.15). Triphenyl phosphate and the toxic tricresyl phosphate can be used as flame-retardant plasticisers for various celluloses and vinyls. Tris 2-ethylhexyl phosphate increases the flame resistance of vinyl sheet and enables it to retain low-temperature flexibility. Cresyldiphenyl phosphate finds use both as a plasticiser and as a flame retardant. 

Triphenyl phosphate n. (C6H5)3P04. A crystalline powder, one of the original synthetic plasticizers for cellulose nitrate. It is also a flame retardant for vinyls, cellulosics, acrylics, and polystyrene. Bp, 410°C mp, 50° C flp, 220°C (428°F). 

Triphenyl phosphate Akzo Nobel Phosflex Cellulose, Polyester, Polystyrene, PVC, UFf, UFr... 

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