Патент USA US3074999код для вставки
United States Patent 0 3,914,989 ICC Patented Jan. 22, 1963 2 1 ?uorobutoxy phosphorus nitrite with sodium thiocyanate is shown: 3,074,939 or TRIMERIC ISOTHIOCYANO ‘POLYFLUORO ALKOXY PHOSPHORUS NITRILES OCHzCFzCFzCFa \ / Rudi F. W. Riitz, Hamden, ‘Conn, assignor to Olin Mathieson Chemicalicorporation, a corporation of Virginia No Drawing.2 giled‘ July 11, 1961, Ser. No. 123,089 0 F30 FrC F2CH2O lainls. (Cl. 260-454) 7 SON This invention relates to trimeric isothiocyano poly \ 10 ?uoroalkoxy phosphorus nitriles and to their preparation. N It has now been found that trimeric isothiocyano poly ?uoroalkoxy phosphorus nitriles can vbe prepared by re H + 3NaCl S action of an alkali metal thiocyanate with a trimeric halo poly?uoroalkoxy phosphorus nitrile. The novel com 15 The novel trimeric isothiocyano polyiluoroalkoxy phos pounds of this invention are sufficiently thermally stable phorus nitriles are prepared in good yields by admixing the that they can be subjected to vacuum distillation for puri? trimeric halo poly?uoroalkoxy phosphorus nitrile with the cation purposes, if desired. '1 alkali metal thiocyanate. In carrying out the reaction ap - ‘ Trimeric halo poly?uoroalkoxy phosphorus nitriles use proximately theoretical quantities of the starting reactants ful as starting materials have the formula: are employed as set forth in the preceding equation al though, if desired, an excess of alkali metal thlocyanate can be employed to insure completion of the reaction. Prefer ably the reaction is carried out in the presence of a com 25 mon solvent for both of the reactants which can be ace tone, acetonitrile etc. The reaction proceeds in general at temperatures between about -—20° C. and about +80° C. When a solvent is employed, the reaction is preferably conducted at the re?ux temperature of the solvent. The 30 reaction time will vary from about 2 minutes to about 1 hour or more depending upon the reaction temperature, the particular solvent employed and the particular react ants utilized. The alkali metal halide formed during the reaction is generally insoluble in the applied solvent. The wherein R1, R2, R3, R4, R5 and R6 are selected from the group consisting of chlorine, bromine, ?uorine, or ~—OCH2(CF2)mY, wherein Y is selected from the group salt can be removed by ?ltration or by washing with consisting of hydrogen or ?uorine, m is an integer of from 1 to 20, wherein in the said nitrile at least one of the water. The new trimeric isothiocyano poly?uoroalkoxy phos~ phorus nitriles are useful in the ?eld of resins and plastics. and at least one of the R1, R2, R3, R4, R5 and R6 sub When heated with bifunctional aliphatic amines of the stituents is chlorine, bromine or ?uorine. Suitable halo 40 general formula NH2(CH2),,NH2 where n is an integer poly?uoroalkoxy phosphorus nitriles for the novel reac of from 2 to 8 inclusive solid polymeric materials with the retained -—P=N—~ ring structure are obtained. Suit tion of this invention include trimeric 1-chloro-l,3,3,5,5 pentakis-alpha, alpha-H,H-tri?uoroethoxy phosphorus ni able bifunctional aliphatic amines include ethylene di R1, R2, R3, R4, R5 and R6 substituents is —-OCH2(CF2)mY trile, trirneric l,3,5~trichloro-1,3,5-tris-alpha, alpha-HH tri?uoroethoxy phosphorus nitrile, trimeric 1,3-dichloro amine, 1,3-diaminopropane, 1,4-diaminopropane, 1,6-di 45 aminohexane, etc. The powdery, polymeric materials ob phosphorus nitrile, 1,1,3,3-tetrachloro-5,Sebis-alpha, alpha, tained by the reaction of the trimeric isothiocyano poly ?uoroalkoxy phosphorus nitriles with hifunctional ali omega-H,H,H~hexa?uorobutoxy phosphorus nitrile, 1 phatic amines can be further subjected to a thermal treat 1,3,5,5-tetrakis - alpha, alpha - H,H - penta?uoropropoxy chloro-1,3,3,5,5-pentakis-alpha, alpha, omega-H,H,H-do deca?uoroheptoxy phosphorus nitrile, 1,1-dichloro-3,3,5,5 tetrakis-alpha, alpha, omega-H,H,H-eicosa?uoroundecan ment yielding glass-like, polymeric materials which are non-in?ammable and practically non-combustible. These glass-like, polymeric materials can be utilized as protec oxy phosphorus nitrile, etc. and the corresponding bromine and ?uorine derivatives. The above-mentioned com pounds can be conveniently prepared by the general tive coatings for metals. Such coated metal products can be formed by dipping the metal article into the molten method described in Ritz et al. United States Patent EXAMPLE I Trimeric 1 ,1 -B is-lsothi0cyan0-3,3,5 ,5 ~Tetrakis-A lpha, 2,876,247. For example, trimeric 1,3-dichloro-1,3,5,5~ tetrakis-alpha, alpha-H,H-hepta?uorobutoxy phosphorus nitrile can be prepared by reacting 1 mole of trimeric phosphonitrilic chloride with 4 moles of the sodium salt of 1,l-H,H-hepta?uorobutanol in toluene at a temperature 60 of about 100° C. The reaction proceeds as set forth in the following equa tion in which, by way of illustration, the reaction between trimeric 1,3,34trichloro-1,5,5-tris-alpha, alpha-I-LH-hepta polymer. Alpha-H,H-Hepta?uorobutoxy Phosphorus N itrile S CN NC S \ / ' \ II / \}II 0 F30 F20 memo-4e CFaCFaCFzC-HzO P——() CI-IzC F2CF2C Fa aoreeee 3 To 8.062 grams of trimeric 1,l-dichloro-3,3,5,S-tetrakis gram of ethylenediamine (98 percent, 0.00412 mole). An exothermic reaction was observed with solidi?cation of the mixture. The slightly yellowish material so obtained was extracted with 50 ml. of hexane and ?nally with the same amount of dry ether. The crude, polymeric, pow dery material thus obtained melted between 122° and alpha, alpha-H,H-hepta?uorobutoxy phosphorus nitrile (0.0082 mole) dissolved in 15 ml. of dry acetone there was added in one portion a solution of 1.72 grams of potas sium thiocyanate (0.165 mole) in 35 ml. of the same sol vent. The resulting reaction mixture was then re?uxed for lO'minutes. On standing overnight the. theoreticalv amount of potassium chloride (1.2 grams), which had precipitated from the reaction mixture, was removed by 124° C. A sample of the polymeric material obtained in the preceding paragraph was subjected to extended heating ?ltration- From the clear ?ltrate the solvent was then 10 at 170° C. in a nitrogen atmosphere. After 3 hours no recovered by distillation and a yellowish, oily residue ad further weight-loss was observed and a glass-like poly mixed with some excess potassium thiocyanate remained. meric material, which was non-inflammable and practi Separation of the oil from the solid was'e?'ected by the cally non-combustible, was obtained. addition of 25 ml. of ether ‘followed by ?ltration. After What is claimed is: removal of the ether in vacuo, the remaining oil was 15 l. Trimeric isothiocyano poly?uoroalkoxy phosphorus purified by vacuum distillation yielding 6.9 grams (782 nitriles of the formula: percent of the theoretical yield)‘ of trimeric 1,1-bis-iso ' thiocyano-3,3,5,5-tetrakis-alpha, alpha-H,H - hepta?uoro butoxy phosphorus nitrile; BP. 149/ 15 1° C. (0.9 mm.), 7192!: 1.3847. The puri?ed product so obtained was. a 20 slightly yellowish, clear oil. The product was analyzed for carbon, hydrogen, nitro~ gen, phosphorus, and sulphur and the following results were obtained: 25 0 n wherein RDVRZ, R3, R4, R5, and R5 are selected from the group consisting of —-—NCS'and --OC_H2(CF2)mY, where: N P s in Y is selected from thegroup consisting of hydrogen and fluorine, is an integer of from 1 to 20, wherein at leastv one of the R1, R2, R3, R4, R5, and R6 substituents is--NCS, and wherein at least one of the R1, R2, R3, R4, R5, and_RB_ Calcd.lorC1sHsFasN5P3S2O4 ________ ._ 20.61 0. 77 7.70 8.90 0.12 'Found_'_ ____________________________ -_ 21.94 0.84 7.09 9.08 5.79 30 substituents is ——OCH2(CF2)mY. EXAMPLE II -”Anfamount-of 4.31 ‘grams of trimeric 1,1-bis-isothio-. alpha-H,H-hepta?uorobutoxy phosphorusnitrile. cyano-3,3,5,5-tetrakis-alpha, alpha-H,H-hepta?uorobutoxy~ phosphorus nitrile (0.00412 mole) was mixed with 0.248 - 2; Trimeric 1,1 - bis-isothiocyano-3,3,5,5-tetralcis-alpha, No references cited.