DE2110769B2 - Perfluoroalkyl phosphoriodides - Google Patents

Description

worm χ = 1 or 2 «t and R, to

37 5 ° / perfluorododecyl 37.5 / "pernuordodecyl

28.5% perfluorotetradecyl 15 6% perfmorhexadecyl 7.6% perfluorooctadecyl 3.7% perfluoroicosyl

18 ° / Perfiuordoco'vl 1,8 / ₀ «srfluonloca.yi

Is 0.8% perfluorotetracosyl.

JiSSS ^ / SL ^ W p. 3 ^. dta

In these cases, conversions of only 15 to 60% are achieved, the reaction proceeds in the case of perfluoroalkyl iodides with a longer carbon chain smooth. At temperatures

antJK about the same size; the corresponding weight fractions would be for the iodides with the R / residue C ₆ F ₁₃ = 43: i. With the aid of gas chromatography the.-R value can be determined to be 42:58. For the

it does not matter whether white or red g «^ ^, ^ _{molar ratio} . ^

the same for non-stoichiometric use. The ^ reactions with C ₄ F ₉ J, C ₆ F ₁₃ J and C ₈ F ₁₇ J must be carried out in a closed vessel, since at the reaction temperatures used, vapor pressures of 20 to 10 atmospheres occur, whereas the reactions of longer-chain perfluoroalkyl iodides are depressurized can be done.

^The preferred starting materials for the reaction _are perfluoroalkyl iodides of the general _formula

30 C ₁ Fe (C ₁ FJ _n J

The invention relates to perfluoroalkylphosphoriodides the general formula

ΓΙ i? ^ Af ^ g perfluoroalkyl radical with Means 4 to 10 carbon atoms and χ = 1 or 2, likewise a mixture of perfluoroalkylphosphoriodides of the general formula

wonn χ = 1 or 2 and R / zu

37.5% perfluorododecyl 28 3 ° / perfluorotetradecyl 15.6% perfluorohexadecyl 7.6% perfluorooctadecyl

Π0 / ρ -fl

i, I / o pernuoreicosyl

1.8% perfluorodocosyl 0.8% / Perflinrtetrarnsvi

The compounds of the invention are derived from the corresponding perfluoroalkyl iodides and elemental Phosphorus produced according to the following equation:

3R / J + 2P = S = R / _£ PJ + R / PJ ₂ (I) (II)

from the known telomerization with tetrafluoroethylene with pentafluoroethyl iodide available (German

see exposition 1915 395). One can both chain pure as well as more accessible and _billi g _e ren kettenverschnittenen perfluoroalkyl iodides one-

set.

To perform the reaction perfluoroalkyl iodides and white or red phosphorus be in a inert gas - for example, nitrogen - flushed reac _tl0ns | _efäß g ^^ n _and at temperatures between ₂ 00 to 28O ⁰ C with intensive mixing several _{stun £} s to sets. The} mixtures obtained from I.

_{and "Kings} are nnt ^ _{s destiUativ getre;} in most cases, however, they are used as such. The alkylphosphoriodides produced in this way in pure form or in mixtures are valuable starting materials for the preparation of the corresponding phosphinic and phosphonic acids (cf. German Offenlegungsschrift 2110 767), on the ^{other hand they are used as} surface-active substances and as dispersants in the production of polytetrafluoroethylene . In this respect, they are clearly superior to the perfluoroetanoic acid previously used for this purpose. As can be seen from the table below, the polymerization of tetrafluoroethylene in the presence of perfluoroalkylphosphonic _{acids and -phosphinic acids proceeds with a space- time yield that is χ} ^ 1QQ0 ^ greater than in the presence of perfluorooctanoic acid. Furthermore, the formation of deposits in the polymerization kettles when using perfluoroalkylphosphonic and phosphinic acids is 30 to 80% less than when using perfluoroalkylcarboxylic acids. This effect is significant insofar as this formation of deposits in the reaction vessels can be the cause of explosions during tetrafluoroethylene polymerization.

Testing of phosphine-phosphonic acids as an emulsifier during polymerization

of tetrafluoroethylene

Space-time yield

1 H.

Deposit formation

/O

C ₄ F ₉ PO ₃ H ₂ / (C ₄ F ₉ ) ₂ PO ₂ H ...

(C ₆ F ₁ J) ₈ i
C _S F ₁₇ PO ₃ H ₂ / (C ₈ F ₁₇ ), PO ₂ H.

C ₁₀ F ₂₁ PO ₃ H ₂

R / PO ₃ H, / R _{/ 2} PO ₂ H

R / = C ₁₂ F ₂₅ to C ₂₄ F ₄₉ *) ..

Compare C ₇ F ₁₅ COOH

140 225 179 188 166

86

1.5 2.5 4.2 2.0 1.1

9.3

20th

*) Manufactured d '-.- ch oxidation of the product mixture from Example 6.

example 1

207 g of perfluorobutyl iodide (= 200 mmol) and 13 g of red phosphorus (200 mg atom) were placed in a 0.5 l autoclave with the exclusion of moisture. The autoclave was flushed with nitrogen and then shaken ^{at 230 ° C. for 12 hours.} There was a pressure of 11 atmospheres. 196.7 g of crude product were obtained which, according to the gas chromatogram, had the following composition:

2.3% = C ₄ F ₉ H

17.0 ° / ₀ = C ₄ F ₉ J (starting substance) 43.8 ^o / o = (C ₄ F,), PJ (2)
33.2%, = C ₁ F ₉ PJ ₂ (1)

3.7% = other

So the conversion was 83%; the yield of 1 and 2 was 94 ° / _0th

In the subsequent distillation through a 40 cm mirror column, C ₄ F ₉ H and C ₄ F ₉ J (identified by 19 F-NMR spectrum) (formed by entrained water) were separated off, products 1 and 2 left at 67 up to 70 ° C / 12 Torr together and are characterized by their 19-F and 31-P-NMR spectra and by their retention value in the gas chromatogram. The two components can be separated by thin layer or column chromatography on silica gel.

Example 2

The yield of 3 and 4 was accordingly 91% with a conversion of 83.5%.

3830 g of the filtered crude product were subjected to vacuum distillation through a 40 cm mirror glass column. A first fraction (398 g) which was identified as perfluorohexyl iodide was recovered at 40 to 60 ° C / 40 torr. Further perfluorohexyl iodide was found in the cold trap in addition to C ₆ F ₁₃ H (total 298 g), which was identified by the 19 F-NMR spectrum. The distillation was then continued at a vacuum of 0.1 torr, the template being cooled with dry ice. Two fractions were collected between 40 and 57 ° C and between 57 and 77 ° C, 1538 and 1488 g, respectively. According to the gas chromatogram and the 31-P and 19-F nuclear magnetic resonance spectrum, the first fraction contained 73% of C ₆ F ₁₃ PJ ₂ and 22% (C _e F ₁₃ ), PJ, the second 86% of (C ₆ F ₁₃ ) ₂ PJ and 12% of C ₆ F ₁₃ PJ ₂ . A distillation residue of 120 g remained, which was not investigated further.

By distillation at higher reflux ratios or by redistillation of the fractions obtained products 3 and 4 can be obtained in pure form.

Example 3

5000 g of perfluorooctyl iodide (= 9.2 mol) and 285 g of red phosphorus (9.2 g atom) were filled into one 5-1 shaking autoclave, closed after flushing with nitrogen one and heated to 235 ° C. A pressure of 8 atm was created. After a reaction time of 12 hours, it was left one cools down. The product obtained was solid and melted to a green-yellow liquid at 40 to 50 ° C with the following composition determined by gas chromatography:

4090 g of perfluorohexyl iodide (= 9.2 mol) and 285 g Red phosphorus (= 9.2 gAtom) was placed in a 5-1 autoclave, then with nitrogen flushed. The autoclave was heated to 230 ° C. and rocked at this temperature for 12 hours. A pressure of 6 atm was created. 270 g of a solid were separated from the crude product, which was made from unreacted Phosphorus and phosphorus iodides. The dark brown filtrate passed "according to the gas chromatogram from the components:

2.6% = C ₀ F ₁₃ H 16.5% = C ₈ F ₁₃ J
43.9% = (C ₆ F ₁₃ ) ₂ PJ (4) 31.9% = C ₀ F ₁₃ PJ ₂ (3)

5.1% = other 4.4% = C ₈ F ₁₇ H
17.9% = C ₈ F ₁₇ J
76.8% = C ₈ F ₁₇ PJ ₂ / (C ₈ F ₁₇ ) ₂ PJ (5/6)

The retention values for C ₈ F ₁₇ PJ ₂ and (C ₈ F ₁₇ ) ₂ PJ coincide here. The assignment and the composition can be confirmed by 31-P and 19-F nuclear magnetic resonance spectra. The yield of 5 and is 94% with a conversion of 82%. _{890 g of C 8} F ₁₇ H and C ₈ F ₁₇ J were distilled off from 5040 g of the crude product at 50 to 55 ° C / 15 Torr. Then at 0.2 torr was further distilled through a 40 cm dish column, the condenser to 5O ⁰ C and thermostated WUR-50 cooled with dry ice to the templates. Two fractions were obtained at 80 to 85 ° C. (1860 g) and at 95 to 115 ° C. (1982 g) and an unexamined residue of 251 g. According to the 31-P and 19-F nuclear magnetic resonance spectra, the first fraction is perfluorooctylphosphorus-55 diiodide and the second fraction is bis-perfluorooctylphosphorus iodide.

Example 4

60 In a 1-1 flask equipped with a reflux condenser, thermometer and stirrer (at 8O ⁰ C.), 500 g of Pernuordecyljodid (0.77 mol) and introduced 24 g of red phosphorus (0.77 mol). The mixture was heated and initially refluxed at 190 ° C. In the

Over the course of 2 hours, the temperature rose to 230 ° C .; it was left at this temperature for 12 hours. The dark liquid solidified into a yellow solid interspersed with excess phosphorus.

The product was dissolved in carbon tetrachloride and the phosphorus filtered off. 290 g (57% of theory) Yellow-colored crystals with a melting point of 90 to 93 ° C. were obtained according to gas chromatography and the 31-P and 19-F nuclear magnetic resonance spectra from an equimolar mixture of Perfluor ^ ecylphosphordijodid and bis-perfluorodecylphosphorjoüid exist. The two components can be separated by thin layer chromatography will.

Example 5

A mixture of perfluoroalkyl iodides, as is the case in the telomerization of tetrafluoroethylene with pentafluoroethyl iodide is obtained, consisting of approximately

1.4% perfluorobutyl iodide,
58.6% perfluorohexyl iodide,
30.3% perfiuorooctyl iodide,

3.8% perfluorodecyl iodide,

was placed together with 14 g of red phosphorus in an autoclave, then kept for 12 hours at 23O ⁰ C; a pressure of 5 atm was created. After filtration, the product was a yellow-brown liquid which fogs a little in air. It is characterized by its nuclear magnetic resonance spectra and by the retention values in the GC.

Example 6

A mixture of perfluoroalkyl iodides (200 g) consisting of approximately

37.3% perfluorododecyl iodide,

28.3% perfluorotetradecyl iodide,

15.6% perfluorohexadecyl iodide,

7.6% perfluorooctadecyl iodide,

3.7% perfluoroicosyl iodide,

1.8% perfluorodocosyl iodide,

0.8% perfluorotetracosyl iodide,

was combined with 8 g of red phosphorus in one

ίο Flask refluxed for 4 hours. The reflux temperature rose to 28O ⁰ C. It remained behind a solid product, which starts to melt at 145 C. The reaction mixture obtained in this way can be converted into a mixture of phosphinic and phosphonic acids by saponification without further purification and thus characterized. This material is an extremely acid-stable surfactant.

To further characterize the novel substances I melting and boiling points, chemical shifts of the nuclear magnetic resonance spectra and retention values of the gas chromatogram were given in ^T able.

The nuclear magnetic resonance spectra were recorded on a Varian HR 100 at 40.5 MHz (31-P) and 94.1 MHz (19-F) recorded. 85% phosphoric acid or trifluoroacetic acid (m = multiplet; b = broad signal).

The gas chromatograms were recorded on a 2 m column (10% silicone grease on Embacel 60 to 100 mesh) by programmed temperature. The elution temperatures (E _T ) of the substances according to the invention are related to those of the perfluoroalkyl iodides C _n F _{2n + 1} J and are given as equivalents of the carbon number η in perfluoroalkyl iodides.

Table I.

at
game link Fp.
( ⁰ C) Kp
730 CC) 31-P-
NMR
(rel. 85% a 19-F-NMR
(rel. CF ₃ COOH CF "groups) Y δ ε ω-1 CF ₃ GC
E _T
standard C _n F _{2n + 1} J
n-equi- Torr (Torr) H ₃ PO ₁ ) 23.5 ß 48.0 3.7 CO valence 1 C ₄ F ₀ PJ ₂ fl. 171 67 to (m) 37.5 113 12.6 70 (m) (12) 24.2 48.0 3.7 (C ₄ F _e ) ₂ PJ (m) 39.0 89 9.7 22.7 (ηϊ> 43.6 44.7 48.3 3.4 2 C ₈ F ₁₃ PJ ₂ fl. 193 55 to -74.4 36.5 136 15.8 57 (0.01) 24 43.6 44.5 48.3 3.9 (C _e F ₁₃ ) ₂ PJ fl. 219 75 to -24.3 (m) 38.2 121 13.6 77 (m) (0.01) 24.7 45.0 45.9 *) 49.7 5.2 3 C ₈ F ₁₇ PJ ₂ 45 to 206 80 to -71.8 37.7 149 17.6 50 85 (0.2) 24 4 ^, 0 45.9 49.7 5.2 (C ₈ F ₁₇ ) ₂ PJ 40 to 258 110 to -24.3 (m) 39 45 115 (m) (0.2) 4th C-10F21PJ2 90 to 240 -72.0 162 19.1 93 (C ₁₀ F ₂₁ ) ₂ PJ -24.8 171 20.4 5 R _{/ a} PJ / RPJ ₂ fl. -73 b R / = C ₁ F ₁ , to -24 b Q0F21 6th R, ₂ PJ / RPJ ₂ 145 to -73 b 175 R / = Ci ₂ F ₂₅ to -25b C ₂₄ F ₄₈ ♦) <5. ε collapses.

Claims (2)

The implementation of perfluoroalkyl iodides with 1 to Fa.en.anspr.ch «: ,. MoraMphosphonodid. de, a ,. _8. ™ i »« n ^hormel R / <3-z) PJx, 2. Mixture of perfluoroalkylphosphoriodides the general formula