Tritolyl phosphates

Acid chlorides are used for the quantitative deterrnination of hydroxyl groups and for acylation of sugars. Industrial appHcations include the formation of the alkyl or aryl carbonates from phosgene (see Carbonic and chloroformic esters) and phosphate esters such as triethyl, triphenyl, tricresyl, and tritolyl phosphates from phosphoms oxychloride. 

Tri-p-tolyl phosphate [20756-92-7, 1330-78-5 (isomeric tritolyl phosphate mixture)] M 368.4, b 232-234 , d 1.16484, n 1.56703. Dried with CaCl2, then distd under vacuum and percolated through a column of alumina. Passage through a packed column at 150°, with a counter-current stream of nitrogen, under reduced pressure, removed residual traces of volatile impurities. 

From Table 5.7 it will be seen that plasticisers for PVC such as the octyl phthalates, tritolyl phosphate and dioctyl sebacate have solubility parameters within 1 cgs unit of that of the polymer. Dimethyl phthalate and the paraffinic oils which are not PVC plasticisers fall outside the range. It will be noted that tritolyl phosphate which gels the most rapidly with PVC has the closest solubility parameter to the polymer. The sebacates which gel more slowly but give products which are flexible at lower temperatures than corresponding formulations from tritolyl phosphate have a lower solubility parameter. It is, however, likely that any difference in the effects of phthalate, phosphate and sebacate plasticisers in... 

Comparison of Table 5.4 and 5.7 allows the prediction that aromatic oils will be plasticisers for natural rubber, that dibutyl phthalate will plasticise poly(methyl methacrylate), that tritolyl phosphate will plasticise nitrile rubbers, that dibenzyl ether will plasticise poly(vinylidene chloride) and that dimethyl phthalate will plasticise cellulose diacetate. These predictions are found to be correct. What is not predictable is that camphor should be an effective plasticiser for cellulose nitrate. It would seem that this crystalline material, which has to be dispersed into the polymer with the aid of liquids such as ethyl alcohol, is only compatible with the polymer because of some specific interaction between the carbonyl group present in the camphor with some group in the cellulose nitrate. 

Because the solubility parameter of tritolyl phosphate is higher than that of dioctyl sebacate, PVC-tritolyl phosphate blends can tolerate more of a low solubility parameter extender than can a corresponding sebacate formulation. 

Figure 6.6. Effect of temperature on the 1000 Hz dielectric constant of stabilised polyfvinyl chloridej-tritolyl phosphate systems. (Copyright 1941 by the American Chemical Society and reprinted by permission of the copyright holder)...

In volume terms the most important class of fire retardants are the phosphates. Tritolyl phosphate and trixylyl phosphate are widely used plasticisers which more or less maintain the fire-retarding characteristics of PVC (unlike the phthalates, which reduce the flame resistance of PVC products). Better results are, however, sometimes obtained using halophosphates such as tri(chloroethyl) phosphate, particularly when used in conjunction with antimony oxide, triphenyl stibine or antimony oxychloride. 

All PVC plasticisers have a solubility parameter similar to that of PVC. It appears that differences between liquids in their plasticising behaviour is due to differences in the degree of interaction between polymer and plasticiser. Thus such phosphates as tritolyl phosphate, which have a high degree of interaction, gel rapidly with polymer, are more difficult to extract with solvents and give compounds with the highest brittle point. Liquids such as dioctyl adipate, with the lowest interaction with polymer, have the converse effect whilst the phthalates, which are intermediate in their degree of interaction, are the best allround materials. 

The solubility parameters of these extenders are generally somewhat lower than that of PVC. They are thus tolerated in only small amounts when conventional plasticisers of low solubility parameter, e.g. the sebacates, are used but in greater amounts when phosphates such as tritolyl phosphate are employed. 

The hydrohalide is liable to dehydrochlorination, particularly when moist acid is used in its preparation, so that hydrochloric acid acceptors such as lead carbonate are useful stabilisers. Dibutyl phthalate and tritolyl phosphate are effective plasticisers. Rubber hydrochloride is used as a packaging film (Pliofilm) and as a rubber-to-metal bonding agent (e.g. Typly). 

Chlorinated rubber is extensively employed in industrial corrosion-resistant surface coatings, for which purpose it is marketed by ICI under the trade name Alloprene. Although thermoplastic moulding compositions have been made by plasticising with the common ester plasticisers such as tritolyl phosphate they are of no commercial importance. 

Plasticised amorphous thermoplastics Certain plastics may be mixed with high-boiling low-volatility liquids to give products of lower T. The most important example occurs with p.v.c. which is often mixed with liquids such as di-iso-octyl phthalate, tritolyl phosphate or other diesters to bring the below room temperature. The resultant plasticised p.v.c. is flexible and to some degree quite rubbery. Other commonly plasticised materials are cellulose acetate and cellulose nitrate. 

More problems are encountered with plasticisers because most extracts from polymer compositions are mixtures and, when separated by TLC, the amount of the individual fractions is often too small for convenient examination by 1H 1-NMR spectroscopy. Moreover, the original plasticisers themselves are often mixtures. For example, tricresyl (tritolyl)phosphate is based on mixed cresols, while most of the higher phthalate esters are based on complex mixtures of alcohols. 

Synonym(s) TCP tritolyl phosphate Xylyl phosphate TXP trixylenyl phosphate Diphenyl tolyl phosphate TPP... 

Organic compounds derived by replacing the hydrogen of an acid by an organic radical or group. Examples of ester plasticisers are tritolyl phosphate, dioctyl phthalate and dioctyl sebacate. ETAD... 

TTP = Tritolyl phosphate TCXP = Tritolyl(xylenyl) phosphate TXP = Trixylenyl phosphate TDP = Tolyl diphenyl phosphate TEPP = Tri(ethylphenyl) phosphate TPP = Triphenyl phosphate TBC = Tributyl citrate BAR = Butyl acetyl ricinoleate MAR = Methyl acetyl ricinoleate... 

Primary plasticizers may be further subdivided. The phthalate types me by far the most popular due to cost and ease of incorporation. Dioctyl phthalate and diisooctyl phthalate are typical of this class, They exhibit good general -purpose properties. Phosphate plasticizers are also important for general-purpose use. Typical of these are tritolyl phosphate and trixylenyl phosphate. These plasticizers also impart fire retardant properties. Low-temperature plasticizers, such as dibntyl sebacate, are used where good low-temperature flexibility is required, For maximum... 

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