SU470963A3 - Method for production of perfluoroalkyl diodophosphines and bis (perfluoroalkyl) iodophosphines - Google Patents

Description

(54) METHOD FOR OBTAINING PERFLUORALKYLD1.YODPHOSPHINES AND BIS- (PERFLUORALKYL) -YODPHOSPHINES

distillations on a mirror column (40 cm) are isolated by C4p9n and (identified by 19-G – S NMR), and products 1 and 2 are distilled at 67-TO C (12 mm Hg) and are characterized by the value their holding capacity by gas chromatogram. Both components can be separated by thin layer chromatography or silica gel column chromatography.

Example 2. 4090 g of perfluorohexyl iodide (9.2 mol) and 285 g of red phosphorus (9.2 gatom) are introduced into a 5 l autoclave, then washed with nitrogen. The autoclave is pagreivaya to 230 ° C and at this temperature it is pumped for 12 hours. The pressure increases to 6 atm. 270 g of a solid substance is separated from the crude product, which consists of perereagirovanny phosphorus and phosphinodiod. A dark brown filtrate on a gas chromatogram reveals the following composition,%;

CeFiaH2,6

CeFisJ16,5

CeFisPJ (4) 43.9

C6Fi3PJ2 (3) 31.9

Other5,1

The yields of products 3 and 4 are respectively 917 ° at 83.5% conversion.

3830 g of filtered crude product is vacuum distilled on a column (40 cm) of polished glass. At 40-60 ° C (40 mmHg), the first fraction (398 g) is obtained, which is identified as perfluorohexyl iodide. The remaining nerfluorohexyl iodide is in the refrigeration trap along with (together 29Üg), which is characterized by 19-F-cneKTpa NMR. Then, under a vacuum of 0.1 mm Hg. Art. further distillation is carried out, the receiver being cooled with dry ice. Lying between 34 and and between 57 and 77C, two fractions, 1536 and 1488, are obtained. The first fraction contains, according to the gas chromatogram, both 31-P and 19-F-cneKTpa NMR 73% C6Fi3PJ2 and 22% (C6Fi3) 2PJ, the second -86% (Sat1 -1: 2p and 12% C5Fi3PJ2- Distillation residue (120 g) was not further investigated.

Pure products 3 and 4 can be obtained by distillation with high ratios of phlegmy or by redistillation of the fractions obtained.

Example 3. 5000 g of perfluorooctyl iodide (9.2 mol) and 285 g of red phosphorus (9.2 gatom) were introduced into a shaking autoclave with a capacity of 5 liters, after washing with nitrogen, closed and heated to 235 ° C.

The pressure increases to 8 atm, after 12 h the reaction autoclave is cooled. The resulting solid product melts at 40-BO C into a yellow-green liquid of the following composition (determined by gas chromatography),%;

CgFnH4,4

CsFnJ17,9

C8Fi7PJ2 / (C8Fl7) 2PJ (5.6) 76.8.

The retention values for CsFi7PJ2 and (CsFi7) 2PJ here coincide. Identity and composition can be confirmed by 31-P and 19-F-CHeKTpa NMR. The yield of products 5 and 6 is 94% with a conversion degree of 82%. From 5040 g of the crude product at 50-55 ° C (15 mmHg), 890 g of C8Fi7n and CsFnJ are distilled off. Then at 0.2 mmHg. Art. further distillation is carried out in a mirror column (40 cm), the refrigerator is thermostatically controlled at 50 ° C and the receiver is cooled with dry ice. Two fractions are obtained at 80–85 ° С (1860 g) and at 95–115 ° С (1982 g) and an unexplored residue (251 g). According to the indications, 31-P and 19-F-cneKTpoB NMR in the first fraction — perfluorooctylphosphindium iodide and in the second — bis- (nerfluorooctyl) -phosphinyiodide.

Example 4. In a flask with a reflux condenser (the temperature is set to 80 ° C) with a capacity of 1 l with a thermometer and a stirrer, 500 g of ер uorfluorodecyl iodide (0.77 mol) and 24 g of red phosphorus (0.77 mol) are introduced. The mixture is heated and refluxed first at 190 ° C with reverse reflux. Within 2 hours the temperature rises to 230 ° C; at this temperature, the mixture is left for 12 hours. The dark liquid solidifies into a yellow solid mass impregnated with excess phosphorus.

The product is dissolved in carbon tetrachloride and filtered from phosphorus. Obtain 290 g (57% of theoretical) yellowish crystals with t. Nl. 90-93 0, which, according to the indications of gas chromatography and 31-P and 19-F-cneKTpoB NMR, consists of an equimolar mixture of a perfluorodecylphosphipyldiodide and bisperfluorodecylphosphine iodide. Both components can be isolated by thin layer chromatography.

Example 5. A mixture of perfluoroalkyl iodides, as it is obtained by teetrization of tetra ({ethylene with pentafluoroethyl iodide, approximate composition,%):

Perfluorobutyl iodide1,4

Perftorheksiliodod58,6

Perfluorooctyl iodide 30.3

Perfluorodecyl iodide 3.8

together with 14 g of red phosphorus, are introduced into the autoclave, then kept at 230 ° C for 12 hours; pressure increases to 5 atm. The product after filtration is a light brown liquid and becomes somewhat smoky in air. It is characterized using NMR spectra and retention values.

Example 6. A mixture of perfluoroalkyl iodides (200 g) of approximate composition,%:

Perfluorododecyl iodide37,3

Perfluorotetradecyl iodid29,3

Perfthexadecyl iodid 15,6

Perfluorooctadecyl 7,7

Perftoreicosyl iodide 3.7

Perfluorodecosyloid1,8

Perf | tortetracosyloid0.8

together with 8 g of red phosphorus is heated in a flask for 4 hours with reverse flow. The temperature of phlegm rises to. A solid remains, which begins to melt at 145 ° C. The reaction mixture thus obtained, without further purification, can be converted by saponification into a mixture of phosphinic and phosphonic acids.

This material is an extremely acid stable surfactant.

For further characterization of the substances according to the invention, the table shows melting and boiling points, chemical shifts in the NMR spectra, as well as

holding capacity of gas chromatograms.

NMR spectra were measured in the HR 100 variant at 40.5 MHz (31-P) or, respectively.

94.1 MHz (19-F). As an external standard, 85% phosphoric acid and, respectively, trifluoroacetic acid (w - multiplet, B - wide signal) were used. Gas chromatographs were temperature-programmed in the column (10% silicone fat on Embacel 60-100 mesh). The elution temperatures (Er) of the substances according to the invention were established in connection with these characteristics for perfluoroalkyl iodides.

CnH2n-i-iJ and, as equivalents, the number of carbon n in perfluoroalkyl iodides was indicated.