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A new family of fluorocarbon polyether fluids were investigated. The results show that these fluids have potential for advanced lubricant and hydraulic fluid applications. The fluid class is thermally stable at 700 deg F, has good lubricating characteristics, and is nonflammable. A shortcoming of these fluids is their corrosive effect on ferrous and titanium alloys in oxidizing atmospheres above 500 deg F.

The mode of action of resins in preventing microbial degradation of cotton cellulose has been investigated using polymer forming fire retardants. Compounds were selected that either react chemically with cellulose or polymerize within cotton fibers without any appreciable linkage between resin and cellulose. With these compounds it was possible to test whether resins mechanically block cellulolytic enzymes through formation of a polymeric barrier at a supra molecular level or whether chemical linkage between the polymer and cellulose is necessary at the molecular level to block susceptible sites on the cellulose molecule. Using enzyme degradation and soil burial techniques, it was shown that both forms of resins protect cotton cellulose in the form of sateen fabric or as cotton sliver., Microbiological Deterioration no. 12.

The present Technical Report No. V, on the work done under the subject contract, covers the quarter June 1 to August 31, 1950. During this period the synthesis and bench scale evaluation of bis-phosphorus compounds have been emphasized in view of the promising leads disclosed during the first year of work. A few preparations have been repeated either because of anomolous early results or because of desire to investigate certain materials further. Attention is now being given to preparative methods amenable to handling in larger scale to provide samples for Motor Laboratory testing and more comprehensive bench scale evaluation. In particular the testing of products not purified by distillation to avoid the need for tedious molecular distillations, is underway. The total numbers of compounds produced this quarter are as follows: phosphine oxides, 1 (total for five quarters, 10); phosphinates, 5 (19); phosphonates, 14 (35, of which 2 are repeats); phosphates 2 (2); miscellaneous (usually as intermediates in preparative procedures), 5 (10); grand total, 27 (76).

The electrochemical reductions and oxidations of organic phosphines, phosphine oxides, and phosphates have been investigated and mechanisms proposed in several cases. It is found that many of the organophosphorous compounds undergo electrode reactions to yield species that are very reactive and hense undergo a cleavage reaction or a following chemical reaction which may be catalytic in nature. Of the compounds investigated bis-(p-nitrophenyl) phosphate and triphenyl-n-butyl phosphonium iodide have shown definite tendency to cleave on reduction, whereas, some others, such as, tris-(pentafluorophenyl) phosphine, diphenyl pentafluorophenyl phosphine, pentafluorobenzene, and decafluorophenyl phosphine oxide undergo reduction with the parent compound regenerated by a following chemical reaction. (Author)

Brief summaries are presented on stereochemical research on the following topics: Synthesis and configuration of phosphine oxides; Hexachlorodisilane: A novel reducing agent for organic oxides and sulfides; Optical purity of phosphines by NMR; Pseudorotation and the stereochemistry of displacement reactions; Stereomutation of phosphine oxides by lithium aluminum hydride; Optical rotatory power; (2,3)-Sigmatropic rearrangements; and Energy barriers in pyramidal inversion process.

Theoretical reasons are advanced for the selection of compounds based on O, N, Si, C, S, and P as coordi ating agents capable of yielding thermally stable chelates. There are no C-to-C bonds in he chelate rings that might be formed by the compounds based on O-S-C-N, O-S-C-S-O, O-Si-C-N, O-Si-O-Si-O, O-Si-C-Si-O, O-Si-C-P-O, O-P-C-N, and O-P-C-P-O patterns selected for investigation. Initial results indicate that the O-P-C-N and O-P-C-P-O patterns are the most promising. T HE AB-type ligands NH2CH2P(O)(OH)R (where R is Me or Ph) and Ph2P(O)CH2P(O)(OH)Ph were synth sized and found to coordinate readily with Zn, yielding chelates with better stability than completely organic AB-type ligands. Other compounds prepared as potential ligands include NH2CH2SO3H, PhCH2SOCH2SOCH2Ph, Me2Si(OH)OSi(OH)Me2, Me2Si(OEt)CH2Si(OEt)Me2, Me2Si(OH)CH2Si(OH)Me2, NH2CH(Ph)P(O)(OH)2, NH2CH2P(O)(OH)2, NH2C(O)P(O)(OH)R (where R is M E OR Ph), and N2CH2P(O)Ph2. (Author)

The preparation of the comple es VO(ClO4)2. 5C5H5NO, VOCl2.2(C6H5)3PO, VO(ClO4)2.4(C6H5)3PO VOCl2.4(C6H5)3 sO, VO ClO4)2.4(C6H5)3 sO, and VOCl2.3(CH3)2SO are reported. Arguments for structural assumptions are based upon measurements of their visible and infrared spec ra, mag etic om s co uc c i pol r solvents. ( u hor)

An infrared method for the rapid screening of candidate catalysts for the polymerization of APO is described. Of the wide variety of chemicals screened, compounds that are acidic under curing conditions are the most effective catalysts. One of these catalysts, diammonium phosphate, combined with APO produces a new durable flame retardant for cellulosic textilium radicals, Ammonhosphoadicals, Phosphates, Imines, Phosphate coat ings, Infrared spectroscopy, Polymers.An infrared method for the rapid screening of candidate catalysts for the polymerization of APO is described. Of the wide variety of chemicals screened, compounds that are acidic under curing conditions are the most effective catalysts. One of these catalysts, diammonium phosphate, combined with APO produces a new durable flame retardant for cellulosic textilium radicals, Ammonium radicals, Phosphates, Imines, Phosphate coat ings, Infrared spectroscopy, Polymers.An infrared method for the rapid screening of candidate catalysts for the polymerization of APO is described. Of the wide variety of chemicals screened, compounds that are acidic under curing conditions are the most effective catalysts. One of these catalysts, diammonium phosphate, combined with APO produces a new durable flame retardant for cellulosic textiles. (Author)