Патент USA US3079441код для вставки
United Etates Pater 3,379,431 Patented Feb. 26, 1953 l. 2 lows: Ten grams of bis(triiluoromethyl)phosphinous amide, (CF3)2PNH2, was transferred in an air-free system 3 079 431 svmrmsrs or retires-hare srsmnarmrono to a three-neck ?ask ?tted with stirrer, Dewar condenser and inlet for gas. About 50 ml. of CHCl3 was then in troduced as a solvent and the ?ask cooled at —30° C. with a Dry-Ice/ acetone bath. The stoichiometric amount of chlorine was introduced through the gas inlet keeping ALKYDPHOdPHlNIC NHREBES Giorgio Tesi and Catherine M. Douglas, Riverside, Calif” asslgnors to the United States of America as represented by the Secretary of the Navy No Brawing. Fiied July 6, 1961, Ser. No. 122,365) 3 Claims. (Cl. 2643-551) (Granted under Title 35, US. Code (1952), see. 26-5) the solution in the ?ask under vigorous stirring. A smooth reaction took place and the whole amount of C12 The invention herein described may be manufactured 10 was used. After the addition was completed, the mixture and used by or for the Government of the United States was slowly treated with two equivalents of the tertiary of America for governmental purposes without the pay amine, trimethylamine. A White precipitate was im ment of any royalties thereon or therefor. mediately formed. The mixture was then allowed to The present invention relates to the preparation of warm up to room temperature. The volatile materials polymeric materials and more particularly to the polymer 15 were then removed under reduced pressure and the white ic materials having a backbone of alternated atoms of solid material left was thoroughly extracted with CHCls phosphorus in the pentavalent state and nitrogen, and in a Soxhlet extractor to remove the trirnethylamine hy having per?uoroalkyl groups as substitutes on the phos drochloride present. The white powder left Was dried phorus. under vacuum. A high yield (about 60%) of a com Materials producw by the synthesis of the present in pound corresponding to the composition [(CF3)2PN]n vention possess remarkable resistance toward oxidation and thermal decomposition, and have uses in any system where these properties are desired. was thus obtained. Other compounds having the same elemental composition but different structure and char acteristics have been isolated from this reaction and are A compound, polymeric bis(per?uoromethyl)phos phinic nitride, has been obtained through decomposition described and claimed in copending application Serial No. 25 122,353, ?led July 6, 1961, for Trimeric and Tetrarneric Bis (Tri?uoromethyl ) Phosphinic Nitrides. Another example of synthesis performed through the of the corresponding azide, (CF3)2PN3, as described in copending patent application Serial No. 97,700, ?led March 22, 1961, for Bisper?uoromethylphosphinic Ni tride. However, due to the exposive character of the procedure of the present invention is the preparation of trimeric ‘bis(hepta?uoropropyl) phosphinic nitride, intermediate azide in the previous method, due care must 30 [C3F7)2PN]3 be taken in preparing the compound by that process. The which was obtained in a 70% yield employing the same synthesis of the present invention overcomes the disad procedure as previously described herein, starting from vantage of the previous method, and di?erent and new bis(hepta?uoropropyl) phosphinous amide, (C3F7)2PNH2. compounds are obtainable thereby. This compound is described and claimed in another co It is an object of the invention to provide a new and 35 improved synthesis for the preparation of compounds having the molecular structure (RF)2PN where R=any per?uoroalkyl groups. It is another object of the invention to provide a com pletely safe technique for synthesizing polymeric bis(per ?uoromethyDphosphinic nitride. pending application, Serial No. 122,354, ?led July 6, 1961, for Trimeric Bis (hepta?uoropropyl)Phosphinic Nitride. The whole operation of the present synthesis is greatly more convenient and practical than the technique of the decomposition of the azide, vand provides entirely safe reactions and yields of high pure grade compound. Obviously many modi?cations and variations of the It is still another object of the invention to provide a present invention are possible in the light of the above synthesis for the preparation of polymeric materials hav teachings. It is therefore to be understood that Within the ing a backbone of alternated atoms of phosphorus in the scope of the appended claims the invention may be prac 45 pentavalent state and nitrogen, and having per?uoroalkyl ticed otherwise than as speci?cally described. groups as substitutes on the phosphorus. What is claimed is: It is a further object of the invention to provide the 1. A method for the synthesis of bis(tri?uoromethyl synthesis of polymeric bis(per?uoroalkyl)phosphinic ni and hepta?uoropropyl)phosphinic nitrides which com trides, wherein the yield is quantitative and the compound prises reacting a chloroform solution of bis(per?uo-ro high in purity. Other objects and many of the attendant advantages of this invention will become readily appreciated as the same alkyl)phosphinous amide of the formula (RF)2PNH2, where RF is from the group consisting of tri?uoromethyl and hepta?uoropropyl, with chlorine at a temperature of becomes better understood by reference to the following —30° C. in an inert atmosphere and subsequent dehydro detailed description: h-alogenation of the reaction mixture with trimethylamine. 55 In the synthesis of the present invention, chlorination 2. A method for the synthesis of bis(tri?uoromethyl) of bis(per?uoroalkyl)phosphinous amides, (RF)2PNH2, phosphinic nitride which comprises reacting a chloroform leads to the formation of bis(per?uoroalkyl) dischloro solution of bis(tri?uoromethyl)phosphinous with chlorine phosphinic amides, (RF)2P(Cl2)NI-I2, which in turn can in an inert atmosphere ‘at a temperature of ——30° C. and be dehydrohalogenated by use of a tertiary amine, such as the subsequent dehydrohalogenation of the reaction mix 60 trimethylamine, thus forming bis (per?uoroalkylphosphin~ ic nitrides, as shown by the following reactions: ture with a trimethylamine. 3. A method for the synthesis of bis(hepta?uoropro pyl)phosphinic nitride comprising reacting a chloroform solution of bis(hepta?uoropropyl)phosphinous amide chlorine in an inert atmosphere at a temperature of where RF=per?uoroalkyl groups, and NR3 may be tri 65 with ——30° C. and the subsequent dehydrohalogenation of the methylamine. reaction mixture with trimethylamine. This technique is completely safe, the yield is quantita tive and the resulting compound can be obtained in high purity by solvent extraction of the tertiary amine hydro chloride from the mixture. References Cited in the ?le of this patent Audrieth et a1. Chemical Reviews, volume 32, pages This can be accomplished 70 125-130 (1940). Harris: J. Chem. Soc. (London), pages 512-519 very easily because of the insolubility of the polymer. An example of the foregoing synthesis is given as fol (1958).